Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom

ABSTRACT

New ligands and compositions with bridged bis-aromatic ligands are disclosed that catalyze the polymerization of monomers into polymers. These catalysts with metal centers have high performance characteristics, including higher comonomer incorporation into ethylene/olefin copolymers, where such olefins are for example, 1-octene, propylene or styrene. The catalysts also polymerize propylene into isotactic polypropylene.

This application is a divisional application of commonly assigned andU.S. application Ser. No. 10,957,036, filed Sep. 30, 2004 now issued asU.S. Pat. No. 7,126,031, which itself is a divisional application ofU.S. application Ser. No. 10/421,212, filed Apr. 23, 2003 now issued asU.S. Pat. No. 6,841,502, which itself claims the benefit of U.S.Provisional Application No. 60/375,363 filed on Apr. 24, 2002, each ofwhich are incorporated herein by reference for all purposes.

FIELD OF THE INVENTION

The present invention relates to ligands, complexes, compositions and/orcatalysts that provide enhanced olefin polymerization capabilities. Thecatalysts are based on bridged bi-aromatic ligands and metal precursorcompositions and/or metal complexes including such ligands combined withactivators (or co-catalysts). The invention also relates to methods ofpolymerization, and in particular to a high-activity solutionpolymerization process. The invention also relates to novel polymers andtheir preparation based on the use of these novel catalysts, includingisotactic polypropylene and methods of preparing isotacticpolypropylene.

BACKGROUND OF THE INVENTION

Ancillary (or spectator) ligand-metal coordination complexes (e.g.,organometallic complexes) and compositions are useful as catalysts,additives, stoichiometric reagents, monomers, solid-state precursors,therapeutic reagents and drugs. Ancillary ligand-metal coordinationcomplexes of this type can be prepared by combining an ancillary ligandwith a suitable metal compound or metal precursor in a suitable solventat a suitable temperature. The ancillary ligand contains functionalgroups that bind to the metal center(s), remain associated with themetal center(s), and therefore provide an opportunity to modify thesteric, electronic and chemical properties of the active metal center(s)of the complex.

Certain known ancillary ligand-metal complexes and compositions arecatalysts for reactions such as oxidation, reduction, hydrogenation,hydrosilylation, hydrocyanation, hydroformylation, polymerization,carbonylation, isomerization, metathesis, carbon-hydrogen activation,carbon-halogen activation, cross-coupling, Friedel-Crafts acylation andalkylation, hydration, dimerization, trimerization, oligomerization,Diels-Alder reactions and other transformations.

One example of the use of these types of ancillary ligand-metalcomplexes and compositions is in the field of polymerization catalysis.In connection with single site catalysis, the ancillary ligand typicallyoffers opportunities to modify the electronic and/or steric environmentsurrounding an active metal center. This allows the ancillary ligand toassist in the creation of possibly different polymers. Group 4metallocene based single site catalysts are generally known forpolymerization reactions. See, generally, “Chemistry of CationicDicyclopentadienyl Group 4 Metal-Alkyl Complexes”, Jordan, Adv.Organometallic Chem., 1991, Vol. 32, pp. 325–153 and the referencestherein, all of which is incorporated herein by reference.

One application for metallocene catalysts is producing isotacticpolypropylene. An extensive body of scientific literature examinescatalyst structures, mechanism and polymers prepared by metallocenecatalysts. See, e.g., Resconi et al., “Selectivity in PropenePolymerization with Metallocene Catalysts,” Chem. Rev. 2000, 100,1253–1345 and G. W. Coates, “Precise Control of PolyolefinStereochemistry Using Single-Site Metal Catalysts,” Chem. Rev. 2000,100, 1223–1252 and the references sited in these review articles.Isotactic polypropylene has historically been produced withheterogeneous catalysts that may be described as a catalyst on a solidsupport (e.g., titanium tetrachloride and aluminum alkyls on magnesiumdichloride). This process typically uses hydrogen to control themolecular weight and electron-donor compounds to control theisotacticity. See also EP 0 622 380, EP 0 292 134 and U.S. Pat. Nos.4,971,936, 5,093,415, 4,297,465, 5,385,993 and 6,239,236.

Given the extensive research activities with respect to metallocenecatalysts, there is continued interested in the next generation ofnon-cyclopentadienyl ligands for olefin polymerization catalystsproviding attractive alternatives. See, e.g., “The Search forNew-Generation Olefin Polymerization Catalysts: Life beyondMetallocenes”, Gibson, et al., Angew. Chem. Int. Ed., 1999, vol. 38, pp.428–447; Organometallics 1999, 18, pp. 3649–3670 and “Advances inNon-Metallocene Olefin polymerization Catalysts”, Gibson, et al., ChemRev. 2003, 103, 283–315. Recently, for isotactic polypropylene,bis-amide catalysts have been disclosed in U.S. Pat. No. 5,318,935 andamidinate catalysts have been disclosed in WO 99/05186. See also U.S.Pat. No. 6,214,939 for non-metallocene isotactic polypropylenecatalysts.

Isotactic polypropylene and its production has been extensively studied.See, e.g., U.S. Pat. No. 6,262,199 for isotactic polypropylene producedwith metallocene catalysts. In general, those of skill in the art haveconcentrated on C₂ symmetrical metal complexes based on the theory thatsuch symmetry allows for tacticity control. See, e.g., “StereospecificOlefin Polymerization with Chiral Metallocene Catalysts”, Brintzinger,et al., Angew. Chem. Int. Ed. Engl., 1995, Vol. 34, pp. 1143–1170. Forexample, Kol et al., J. Am. Chem. Soc. 2000, 122, 10706–10707 and WO02/36638 disclose a C₂-symmetrical structure that may induce tacticitycontrol. However, the art still fails to provide a highermolecular-weight, narrow polydispersity, isotactic polypropylene with ahigh melting point, in part provided by an isotactic polypropylenehaving few, if any, regio-errors (or regio-irregularities), produced athigh temperatures (e.g., greater than 100° C.) that is commerciallydesirable.

Therefore, a need exists for the discovery and optimization ofnon-cyclopentadienyl based catalysts for olefin polymerization, and inparticular for certain polymers, such as isotactic polypropylene andethylene-alpha-olefin copolymers. Furthermore, a need still exists fornew catalysts to produce high molecular weight isotactic polypropylenewith a high melting point, particularly in a solution process and athigher polymerization temperatures.

SUMMARY OF THE INVENTION

This invention provides a resolution to these needs. This inventiondiscloses enhanced catalytic performances for olefin polymerization whencertain ligands are employed in a catalyst, where the ligands aredianionic chelating ligands that can occupy up to four coordinationsites of a metal atom and more specifically have a bridged-bis-bi-arylstructure. In addition, some of the ligands, metal complexes andpolymers disclosed herein are themselves novel.

This invention discloses catalysts, compositions and complexes(including activated complexes) based on certain bridged bis-bi-aromaticancillary ligands. For example, the compositions of this inventioncomprise a ligand and a metal precursor and optionally an activator. Insome embodiments, the ligands and the method of making the ligands isalso part of this invention.

The catalysts in some embodiments are compositions comprising the ligandand metal precursor, and optionally may additionally include anactivator, combination of activators or activator package. In otherembodiments, the catalysts are metal-ligand complexes and optionally mayadditionally include an activator, combination of activators oractivator package. For example, the metal-ligand complexes of thisinvention can be characterized by the general formula:(4,2,O,S)ML_(n),  (VI)where (4,2,O,S) is a dianionic ligand having at least 4 atoms that areoxygen or sulfur and chelating to the metal M at at least 2, morespecifically 4, coordination sites through oxygen and/or sulfur atoms; Mis a metal selected from the group consisting of groups 3–6 andLanthanide elements of the Periodic Table of Elements, morespecifically, from group 4 (Hf. Zr and Ti); L is independently selectedfrom the group consisting of halide (F, Cl, Br, I), optionallysubstituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl,heteroalkynyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, alkylthio, arylthio, nitro, hydrido, allyl, diene,phosphine, carboxylates, 1,3-dionates, oxalates, carbonates, nitrates,sulphates, ethers, thioethers and combinations thereof; and optionallytwo or more L groups may be linked together in a ring structure; n′ is1, 2, 3, or 4.

In another aspect of the invention, a polymerization process isdisclosed for monomers. The polymerization process involves subjectingone or more monomers to the catalyst compositions or complexes of thisinvention under polymerization conditions. The polymerization processcan be continuous, batch or semi-batch and can be homogeneous, supportedhomogeneous or heterogeneous. Another aspect of this invention relatesto arrays of ligands, metal precursors and/or metal-ligand complexes.These arrays are useful for the high speed or combinatorial materialsscience discovery or optimization of the catalyst compositions orcomplexes disclosed herein.

In particular, a method of producing isotactic polypropylene in asolution process is disclosed and is surprisingly tunable based on thepolymerization conditions, activators and substituents on the catalyst.Other polymerization processes that are tunable based on the samecriteria are the copolymerization of ethylene and styrene (orsubstituted styrene) and ethylene and other alpha-olefins with highincorporation of styrene or the alpha-olefin.

Thus, it is an object of this invention to polymerize olefins andunsaturated monomers using metal-ligand complexes. It is also an objectof this invention to polymerize olefins and unsaturated monomers usingcompositions including certain bridged bis-aromatic ligands and metalprecursors and/or bridged bis-aromatic ligand-metal complexes.

It is still a further object of this invention to polymerize olefins andunsaturated monomers with the metal-ligand complexes that additionallycomprise an activator or combination of activators.

It is also an object of this invention to use non-metallocene group 4complexes as polymerization catalysts for the production of isotacticpolypropylene or other polymers.

Further objects and aspects of this invention will be evident to thoseof skill in the art upon review of this specification.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 a is an X-ray crystal structure of the compound identified hereinas C5 and FIG. 1 b is an alternate view of the same crystal structure.

FIG. 2, including parts A, B, C and D, is a spectrum comparing variousisotactic polypropylene polymers made in accord with this invention,some with regio-errors and others without detectible regio-errors.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the phrase “characterized by the formula” is notintended to be limiting and is used in the same way that “comprising” iscommonly used. The term “independently selected” is used herein toindicate that the R groups, e.g., R¹, R², R³, R⁴, and R⁵ can beidentical or different (e.g. R¹, R², R³, R⁴, and R⁵ may all besubstituted alkyls or R¹ and R² may be a substituted alkyl and R³ may bean aryl, etc.). Use of the singular includes use of the plural and viceversa (e.g., a hexane solvent, includes hexanes). A named R group willgenerally have the structure that is recognized in the art ascorresponding to R groups having that name. The terms “compound” and“complex” are generally used interchangeably in this specification, butthose of skill in the art may recognize certain compounds as complexesand vice versa. For the purposes of illustration, representative certaingroups are defined herein. These definitions are intended to supplementand illustrate, not preclude, the definitions known to those of skill inthe art.

“Optional” or “optionally” means that the subsequently described eventor circumstance may or may not occur, and that the description includesinstances where said event or circumstance occurs and instances where itdoes not. For example, the phrase “optionally substituted hydrocarbyl”means that a hydrocarbyl moiety may or may not be substituted and thatthe description includes both unsubstituted hydrocarbyl and hydrocarbylwhere there is substitution.

The term “alkyl” as used herein refers to a branched or unbranchedsaturated hydrocarbon group typically although not necessarilycontaining 1 to about 50 carbon atoms, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, aswell as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like.Generally, although again not necessarily, alkyl groups herein maycontain 1 to about 12 carbon atoms. The term “lower alkyl” intends analkyl group of one to six carbon atoms, specifically one to four carbonatoms. “Substituted alkyl” refers to alkyl substituted with one or moresubstituent groups (e.g., benzyl or chloromethyl), and the terms“heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl in whichat least one carbon atom is replaced with a heteroatom (e.g., —CH₂OCH₃is an example of a heteroalkyl).

The term “alkenyl” as used herein refers to a branched or unbranchedhydrocarbon group typically although not necessarily containing 2 toabout 50 carbon atoms and at least one double bond, such as ethenyl,n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, andthe like. Generally, although again not necessarily, alkenyl groupsherein contain 2 to about 12 carbon atoms. The term “lower alkenyl”intends an alkenyl group of two to six carbon atoms, specifically two tofour carbon atoms. “Substituted alkenyl” refers to alkenyl substitutedwith one or more substituent groups, and the terms“heteroatom-containing alkenyl” and “heteroalkenyl” refer to alkenyl inwhich at least one carbon atom is replaced with a heteroatom.

The term “alkynyl” as used herein refers to a branched or unbranchedhydrocarbon group typically although not necessarily containing 2 toabout 50 carbon atoms and at least one triple bond, such as ethynyl,n-propynyl, isopropynyl, n-butynyl, isobutynyl, octynyl, decynyl, andthe like. Generally, although again not necessarily, alkynyl groupsherein may have 2 to about 12 carbon atoms. The term “lower alkynyl”intends an alkynyl group of two to six carbon atoms, specifically threeor four carbon atoms. “Substituted alkynyl” refers to alkynylsubstituted with one or more substituent groups, and the terms“heteroatom-containing alkynyl” and “heteroalkynyl” refer to alkynyl inwhich at least one carbon atom is replaced with a heteroatom.

The term “alkoxy” as used herein intends an alkyl group bound through asingle, terminal ether linkage; that is, an “alkoxy” group may berepresented as —O-alkyl where alkyl is as defined above. A “loweralkoxy” group intends an alkoxy group having one to six, morespecifically one to four, carbon atoms. The term “aryloxy” is used in asimilar fashion, with aryl as defined below. The term “hydroxy” refersto —OH.

Similarly, the term “alkylthio” as used herein intends an alkyl groupbound through a single, terminal thioether linkage; that is, an“alkylthio” group may be represented as —S-alkyl where alkyl is asdefined above. A “lower alkyl thio” group intends an alkyl thio grouphaving one to six, more specifically one to four, carbon atoms. The term“arylthio” is used similarly, with aryl as defined below. The term“thioxy” refers to —SH.

The term “allenyl” is used herein in the conventional sense to refer toa molecular segment having the structure —CH═C═CH₂. An “allenyl” groupmay be unsubstituted or substituted with one or more non-hydrogensubstituents.

The term “aryl” as used herein, and unless otherwise specified, refersto an aromatic substituent containing a single aromatic ring or multiplearomatic rings that are fused together, linked covalently, or linked toa common group such as a methylene or ethylene moiety. More specificaryl groups contain one aromatic ring or two or three fused or linkedaromatic rings, e.g., phenyl, naphthyl, biphenyl, anthracenyl,phenanthrenyl, and the like. In particular embodiments, arylsubstituents have 1 to about 200 carbon atoms, typically 1 to about 50carbon atoms, and specifically 1 to about 20 carbon atoms. “Substitutedaryl” refers to an aryl moiety substituted with one or more substituentgroups, (e.g., tolyl, mesityl and perfluorophenyl) and the terms“heteroatom-containing aryl” and “heteroaryl” refer to aryl in which atleast one carbon atom is replaced with a heteroatom (e.g., rings such asthiophene, pyridine, isoxazole, pyrazole, pyrrole, furan, etc. orbenzo-fused analogues of these rings are included in the term“heteroaryl”). In some embodiments herein, multi-ring moieties aresubstituents and in such an embodiment the multi-ring moiety can beattached at an appropriate atom. For example, “naphthyl” can be1-naphthyl or 2-naphthyl; “anthracenyl” can be 1-anthracenyl,2-anthracenyl or 9-anthracenyl; and “phenanthrenyl” can be1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl or9-phenanthrenyl.

The term “aralkyl” refers to an alkyl group with an aryl substituent,and the term “aralkylene” refers to an alkylene group with an arylsubstituent; the term “alkaryl” refers to an aryl group that has analkyl substituent, and the term “alkarylene” refers to an arylene groupwith an alkyl substituent.

The terms “halo” and “halogen” are used in the conventional sense torefer to a chloro, bromo, fluoro or iodo substituent. The terms“haloalkyl,” “haloalkenyl” or “haloalkynyl” (or “halogenated alkyl,”“halogenated alkenyl,” or “halogenated alkynyl”) refers to an alkyl,alkenyl or alkynyl group, respectively, in which at least one of thehydrogen atoms in the group has been replaced with a halogen atom.

The term “heteroatom-containing” as in a “heteroatom-containinghydrocarbyl group” refers to a molecule or molecular fragment in whichone or more carbon atoms is replaced with an atom other than carbon,e.g., nitrogen, oxygen, sulfur, phosphorus, boron or silicon. Similarly,the term “heteroalkyl” refers to an alkyl substituent that isheteroatom-containing, the term “heterocyclic” refers to a cyclicsubstituent that is heteroatom-containing, the term “heteroaryl” refersto an aryl substituent that is heteroatom-containing, and the like. Whenthe term “heteroatom-containing” appears prior to a list of possibleheteroatom-containing groups, it is intended that the term apply toevery member of that group. That is, the phrase “heteroatom-containingalkyl, alkenyl and alkynyl” is to be interpreted as“heteroatom-containing alkyl, heteroatom-containing alkenyl andheteroatom-containing alkynyl.”

“Hydrocarbyl” refers to hydrocarbyl radicals containing 1 to about 50carbon atoms, specifically 1 to about 24 carbon atoms, most specifically1 to about 16 carbon atoms, including branched or unbranched, saturatedor unsaturated species, such as alkyl groups, alkenyl groups, arylgroups, and the like. The term “lower hydrocarbyl” intends a hydrocarbylgroup of one to six carbon atoms, specifically one to four carbon atoms.“Substituted hydrocarbyl” refers to hydrocarbyl substituted with one ormore substituent groups, and the terms “heteroatom-containinghydrocarbyl” and “heterohydrocarbyl” refer to hydrocarbyl in which atleast one carbon atom is replaced with a heteroatom.

By “substituted” as in “substituted hydrocarbyl,” “substituted aryl,”“substituted alkyl,” “substituted alkenyl” and the like, as alluded toin some of the aforementioned definitions, is meant that in thehydrocarbyl, hydrocarbylene, alkyl, alkenyl, aryl or other moiety, atleast one hydrogen atom bound to a carbon atom is replaced with one ormore substituents that are functional groups such as hydroxyl, alkoxy,alkylthio, phosphino, amino, halo, silyl, and the like. When the term“substituted” appears prior to a list of possible substituted groups, itis intended that the term apply to every member of that group. That is,the phrase “substituted alkyl, alkenyl and alkynyl” is to be interpretedas “substituted alkyl, substituted alkenyl and substituted alkynyl.”Similarly, “optionally substituted alkyl, alkenyl and alkynyl” is to beinterpreted as “optionally substituted alkyl, optionally substitutedalkenyl and optionally substituted alkynyl.”

By “divalent” as in “divalent hydrocarbyl”, “divalent alkyl”, “divalentaryl” and the like, is meant that the hydrocarbyl, alkyl, aryl or othermoiety is bonded at two points to atoms, molecules or moieties with thetwo bonding points being covalent bonds. The term “aromatic” is used inits usual sense, including unsaturation that is essentially delocalizedacross multple bonds, such as around a ring.

As used herein the term “silyl” refers to the —SiZ¹Z²Z³ radical, whereeach of Z¹, Z², and Z³ is independently selected from the groupconsisting of hydride and optionally substituted alkyl, alkenyl,alkynyl, heteroatom-containing alkyl, heteroatom-containing alkenyl,heteroatom-containing alkynyl, aryl, heteroaryl, alkoxy, aryloxy, amino,silyl and combinations thereof.

As used herein the term “boryl” refers to the —BZ¹Z² group, where eachof Z¹ and Z² is as defined above. As used herein, the term “phosphino”refers to the group —PZ¹Z², where each of Z¹ and Z² is as defined above.As used herein, the term “phosphine” refers to the group: PZ¹Z²Z³, whereeach of Z¹, Z³ and Z² is as defined above. The term “amino” is usedherein to refer to the group —NZ¹Z², where each of Z¹ and Z² is asdefined above. The term “amine” is used herein to refer to the group:NZ¹Z²Z³, where each of Z¹, Z² and Z³ is as defined above.

The term “saturated” refers to lack of double and triple bonds betweenatoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, andthe like. The term “unsaturated” refers to the presence of one or moredouble and triple bonds between atoms of a radical group such as vinyl,acetylide, oxazolinyl, cyclohexenyl, acetyl and the like.

Other abbreviations used herein include: “^(i)Pr” to refer to isopropyl;“^(t)Bu” to refer to tertbutyl; “Me” to refer to methyl; “Et” to referto ethyl; and “Ph” refers to phenyl.

The ligands that are suitable for use in the catalysts herein haveseveral general, alternative descriptions. In one embodiment, theligands are dianionic, chelating ligands that may occupy up to fourcoordination sites of a metal atom. The ligands can also be described asdiaionic ligands that, when chelated to a metal atom, form at least oneor two seven member metalocycles (counting the metal atom as one memberof the seven member ring). Also, in some embodiments, the ligands can bedescribed as dianionic, chelating ligands that use either oxygen orsulfur as binding atoms to the metal atom. In still other embodiments,the ligands can be described as non-metallocene ligands that cancoordinate in an approximate C₂-symmetcial complex with a metal atom.These embodiments can be used together or separately.

For example, suitable ligands useful in this invention may becharacterized by the following general formulas:

wherein each ligand has at least two hydrogen atoms capable of removalin a binding reaction with a metal atom or metal precursor or base; ARis an aromatic group that can be the same or different from the other ARgroups with, generally, each AR being independently selected from thegroup consisting of optionally substituted aryl or heteroaryl; B is abridging group having from one to 50 atoms (not counting hydrogenatoms); X and X′ are the same or different and are independentlyselected from the group consisting of oxygen, sulfur, —NR³⁰—, —PR³⁰—,where R³⁰ is selected from the group consisting of hydride, halide, andoptionally substituted hydrocarbyl, heteroatom-containing hydrocarbyl,silyl, boryl, alkoxy, aryloxy and combinations thereof; X″ and X′″ arethe same or different and are independently selected from the groupconsisting of optionally substituted amino, phosphino, hydroxy, alkoxy,aryloxy, thioxy, alkylthio and arylthio; Y and Y′ are the same ordifferent and are independently selected from the group consisting ofoptionally substituted amino, phosphino, hydroxy, alkoxy, aryloxy,thioxy, alkylthio and arylthio; when the AR group attached to the bridgeis an optionally substituted heteroaryl, X and/or X′ can be part of thearomatic ring. The difference between formulas I and II are that thebridge is either directly attached to the aromatic ring (formula II) oris attached to the aromatic ring via the X and/or X′ group (formula I).

In formula I and formula II, it is required that there be at least 2hydrogen atoms associated with each ligand that are capable of beingremoved in a complexation reaction with a metal atom or metal precursoror base. In some embodiments, prior to such a complexation reaction, abase may be reacted with the ligand to form a salt, the product of whichmay then be reacted with a metal precursor (as described herein). Insome embodiments at least two of X, X′, Y and Y′ or at least two of X″,X′″, Y and Y′ have at least one hydrogen atom. In some embodiments, R³⁰is selected from the group consisting of hydride and optionallysubstituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl,heteroalkynyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thioxy, alkylthio, arylthio, halide, nitro, andcombinations thereof. In some embodiments, X and X′ are independentlyselected from the group consisting of oxygen, sulfur and —NR³⁰—; and instill other embodiments X and X′ are independently selected from thegroup consisting of oxygen and sulfur. In some embodiments, Y and Y′ areselected from the group consisting of amino, hydroxy, alkoxy, aryloxy,thioxy, alkylthio and arylthio; and in still other embodiments Y and Y′are independently selected from the group consisting of hydroxy andthioxy.

Generally, the “upper aromatic ring” is the ring to which a Y group(such as Y, Y′) is bonded or part of. Similarly, the “lower aromaticring” is the ring to which an X group (such as X, X′, X″, etc.) isbonded or part of. In some embodiments, at least one AR is aheteroaromatic and more specifically a heteroaryl group. In otherembodiments, at least one upper aromatic ring is a heteroaromatic andmore specifically a heteroaryl. Other embodiments include those where atleast one lower aromatic ring is a heteroaromatic and more specificallya heteroaryl.

In some embodiments, the bridging group B is selected from the groupconsisting of optionally substituted divalent hydrocarbyl and divalentheteroatom containing hydrocarbyl. In other embodiments, B is selectedfrom the group consisting of optionally substituted divalent alkyl,alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl,heteroaryl and silyl. In still other embodiments, B can be representedby the general formula -(Q″R⁴⁰ _(2-z″)) _(z′)— wherein each Q″ is eithercarbon or silicon and each R⁴⁰ may be the same or different from theothers such that each R⁴⁰ is selected from the group consisting ofhydride and optionally substituted hydrocarbyl, and optionally two ormore R⁴⁰ groups may be joined into a ring structure having from 3 to 50atoms in the ring structure (not counting hydrogen atoms); and z′ is aninteger from 1 to 10, more specifically from 1–5 and even morespecifically from 2–5 and z″ is 0, 1 or 2. For example, when z″ is 2,there is no R⁴⁰ groups associated with Q″, which allows for those caseswhere one Q″ is multiply bonded to a second Q″. In more specificembodiments, R⁴⁰ is selected from the group consisting of hydride,halide, and optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl,heteroalkenyl, heteroalkynyl, aryl, heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thioxy, alkylthio, arylthio, andcombinations thereof. Specific B groups within these embodiments include—(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, and —(CH₂)—(C₆H₄)—(CH₂)—. Other specificbridging moieties are set forth in the example ligands and complexesherein.

In other embodiments, the ligands can be characterized by the generalformula:

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰ is independently selected from thegroup consisting of hydride, halide, and optionally substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, alkoxy, aryloxy, silyl,boryl, phosphino, amino, thioxy, alkylthio, arylthio, nitro, andcombinations thereof; optionally two or more R groups can combinetogether into ring structures (for example, single ring or multiple ringstructures), with such ring structures having from 3 to 12 atoms in thering (not counting hydrogen atoms); B is a bridging group having fromone to 50 atoms (not counting hydrogen atoms); X and X′ and Y and Y′ areas defined above. The notation —Y, —Y′, —X and —X′ is intended to meanthat the group can be part of the aromatic ring (forming a heteroaryl)and/or replace one or more of the R groups (R¹–R²⁰). The notation forthe bridging group B (∪B∪) can be combined with either or both —X and—X′ or the bridging group can replace one or more of the R groups on theindictated structure (e.g., such as R⁹ and/or R¹⁹). In those embodimentswhere the bridging group B is not combined with the —X and/or —X′ group,X and X′ are defined as X″ and X′″, above.

In more specific embodiments, each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁵, R¹⁶, R¹⁷, R¹⁹, and R²⁰ isindependently selected from the group consisting of hydride, halide, andoptionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl,aryloxyl, silyl, boryl, phosphino, amino, thioxy, alkylthio, arylthio,nitro, and combinations thereof. In even more specific embodiments, eachof R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰ is independently selected from the groupconsisting of hydride, halide, and optionally substituted alkyl,heteroalkyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, amino,alkylthio and arylthio. In some embodiments, at least one of R² and R¹²is not hydrogen and in still other embodiments both R² and R¹² are nothydrogen.

In more specific embodiments, the ligands useful in this invention canbe characterized by the formula:

wherein R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, and R¹⁹ are as defined above, B is as defined above, X and X′ areas defined above, and Y and Y′ are as defined above with the provisothat each of Y and Y′ include hydrogen.

In more specific embodiments, the ligands useful in this invention canbe characterized by the formula:

In formula (V), the bridging group has been made part of the X moietiesand the bis-aryl moieties have been made the same as each other. The Ymoieties again include hydrogen. In addition, in formula (V), each ofR², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ is independently selected from thegroup consisting of hydride, halide, and optionally substituted alkyl,alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl,heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thioxy,alkylthio and arylthio, nitro, and combinations thereof.

Specific ligands within the scope of this invention include:

In some embodiments the choice of X, X′, Y, Y′, R², R¹² and B have astrong influence on the production of isotactic polypropylene in asolution process. Specific ligands within the scope of thisparticularization include for example: LL1–LL10, LL12–LL23, LL26–LL32,LL37–LL40, LL45–LL49 and LL52–LL57.

In some embodiments, the size and identity of the substituents on theAR-Y and AR-Y′, such as the R² and/or R¹² groups, has an influence onthe production of isotactic polypropylene in a solution process,allowing for a range of isotactic polypropylene polymers to be preparedwith desired properties. Thus, in such embodiments, R² and R¹² are bulkysubstituents and may be independently selected from the group consistingof optionally substituted cycloalkylaryl, aryl and heteroaryl. Morespecifically, each R² and/or R¹² is independently selected from thegroup consisting of optionally substituted aryl and heteroaryl. SpecificR² and/or R¹² groups include carbozole, 3,5-bis-tert-butyl-phenyl,1,2,3,4,5,6,7,8-octahydroanthacenyl, 1-naphthyl, 9-anthracenyl and2,4,6-trimethylphenyl. Specific ligands within the scope of thisparticularization for bulky substituents include:

In some embodiments, the size and identity of the substituents on theupper aromatic ring (e.g., AR-X and AR-X′), such as the R⁷ and/or R¹⁷groups, has an influence on the production of isotactic polypropylene ina solution process, allowing for a range of isotactic polypropylenepolymers to be prepared with desired properties. Thus, in suchembodiments, R⁷ and R¹⁷ may be independently selected from the groupconsisting of halo and optionally substituted hydrocarbyl, alkoxy,aryloxy, dialkyl- or diarylamino, alkyl- or arylthio. Similarly in suchembodiments, R⁴ and R¹⁴ may be independently selected from the groupconsisting of halo and optionally substituted hydrocarbyl, alkoxy,aryloxy, dialkyl- or diarylamino, alkyl- or arylthio. Specific ligandswithin the scope of this particularization include:

Certain of the ligands are novel compounds and those of skill in the artwill be able to identify such compounds from the above. Also, certainembodiments of these ligands are preferred for the polymerization ofcertain monomers in a catalytic composition and/or in a metal complex.These certain embodiments are discussed further below.

In some embodiments, the ligands of the invention may be prepared usingknown procedures. See, for example, Advanced Organic Chemistry, March,Wiley, New York 1992 (4^(th) Ed.). Specifically, the ligands of theinvention may be prepared using a variety of synthesis routes, dependingon the variation desired in the ligand. In general, building blocks areprepared that are then linked together with a bridging group. Variationsin the R group substituents can be introduced in the synthesis of thebuilding blocks. Variations in the bridge can be introduced with thesynthesis of the bridging group.

Specific ligands within the scope of this invention may be preparedaccording to the general schemes shown below, where building blocks(designated BB) are first prepared and then coupled together. There areseveral different ways to use these building blocks. In one embodiment,generally, each of the optionally substituted phenyl rings is preparedas a separate building block (schemes 1 (a and b) and 2). The desiredoptionally substituted phenyls are then combined into bi-phenyl buildingblocks (schemes 3 and 4), which are then bridged together (schemes 7, 8,9, and 10). In another embodiment, the optionally substituted phenylbuilding blocks are bridged together (schemes 5 and 6) and thenadditional optionally substituted phenyl building blocks are added toform the bridged bi-aryl structures (schemes 11, 12, 13, and 14). Inaddition, schemes to effect certain substitutions on the phenyl groupsare included (schemes 15, 16, 17 and 18). In many of these schemes,cross coupling reactions are used (e.g., Suzuki, Negishi orBuchwald-Hartwig cross coupling). These cross coupling reactions aregenerally known in the art; for example, see Tetrahedron, 1998, 54(3/4),263–303 and J. Am. Chem. Soc. 2001, 123(31), 7727–7729. The startingmaterials or reagents used in these schemes are generally commerciallyavailable, or are prepared via routine synthetic means.

To facilitate the description of the ligand synthesis techniques used,following are some abbreviations that are used in this description(including the schemes): PG=“protecting group”, which typically means aphenol or thiophenol protecting group including, but not limited to:methyl (Me), benzyl (Bn), substituted benzyl (2-methoxyphenylmethyl:MPM,etc.), alkoxymethyl (methoxymethyl:MOM, etc.), tetrahydropyranyl (THP),silyl (trimethylsilyl:TMS, tert-butyldimethylsilyl:TBS, etc.) and allyl(Allyl); LG=“leaving group”=leaving group for nucleophilic displacementreactions group including, but not limited to: chloro, bromo, iodo,tosyl (para-toluenesulfonyl) and triflic (trifluoromethylsulfonyl). Thesymbol

depicts a bridging moiety as defined elsewhere in this specification.The term “upper phenyl ring” is used consistently with the term “upperaromatic ring”, described above. The term “lower phenyl ring” is usedconsistently with the term “lower aromatic ring”, described above.

Scheme 1a below is a general building block synthesis scheme,specifically depicting the synthesis of Y-protected, 2-bromosubstituted, upper phenyl ring building blocks:

As shown in Scheme 1a, a protecting group (PG) is used to prepare theappropriate building block (BB(a)). The substituents on the buildingblock are as defined above. The variables R and R′ are generallyselected from the same group as R², and may be optionally substitutedalkyl, aryl, amino and the like; optionally R and R′ may be linked orfused. “Appropriate cross-coupling reaction conditions” are generallyknown to those of skill in the art, and may be found in the above-citedreferences. Other reaction conditions will be known to those of skill inthe art, with reference to the examples herein.

As an alternative, Scheme 1b shows a general synthesis scheme forY-protected, 2-bromo substituted, upper phenyl ring building blocks:

In scheme 1b, the variables are defined as discussed above.

Scheme 2 below is a general scheme for the synthesis of X-protected2-boronic ester substituted lower phenyl ring building blocks,X-protected 2-ZnCl substituted lower-ring building blocks, andX-deprotected 2-boronic acid substituted lower ring building blocks:

In scheme 2, the variables are defined as discussed above. In additionthe phrase “cat. H⁺” refers to an acid catalyzed reaction that suppliesa hydrogen ion, such as p-toluenesufonic acid (TsOH) or hydrochloricacid (HCl), as is known to those of skill in the art.

Scheme 3 below is a general scheme for the synthesis of Y-protectedupper phenyl ring, X-deprotected lower phenyl ring building block:

In scheme 3, the variables are defined as discussed above.

Scheme 4 below is a general scheme for the synthesis of 2-bromosubstituted, Y-protected upper phenyl ring, X-deprotected lower phenylring building block:

In scheme 4, the variables are defined as discussed above.

Scheme 5 below is a general scheme for the synthesis of symmetric 2-Brsubstituted, 2-boronic ester-substituted and 2-ZnCl-substituted, bridgedlower phenyl ring building blocks:

In scheme 5, the variables are defined as discussed above. In additionthe phrase “base” refers to bases in general (such as cesium carbonateor potassium tert-butoxide), as is known to those of skill in the art.Also the phrase “cat. Pd(0)” refers to a catalyst that uses aligand-stabilized Pd⁰ complex, known to those of skill in the art.

Scheme 6 below is a general scheme for the synthesis of unsymmetric 2-Brsubstituted, 2-boronic ester-substituted and 2-ZnCl-substituted, bridgedlower phenyl ring building blocks:

In scheme 6, the variables are defined as discussed above.

Scheme 7 below is a general scheme for the synthesis of symmetricY-protected, upper phenyl ring 2-bromo-substituted, lower phenyl ringbridged building blocks:

In scheme 7, the variables are defined as discussed above.

Scheme 8 below is a general scheme for the synthesis of unsymmetricY,Y′-protected, upper phenyl ring 2-bromo-substituted, lower phenyl ringbridged building blocks:

In scheme 8, the variables are defined as discussed above.

Scheme 9 below is a general scheme for the double reaction of buildingblock BB(e) with bridge, followed by deprotection:

In scheme 9, the variables are defined as discussed above.

Scheme 10 below is a general scheme for the sequential reaction ofbuilding blocks BB(e) and BB(f) with bridge, followed by deprotection:

In scheme 10, the variables are defined as discussed above.

Scheme 11 below is a general scheme for the conversion of building blockBB(a) to a boronic ester or ZnCl derivative, followed by doublecross-coupling with building block BB(g) and subsequent deprotection:

In scheme 11, the variables are defined as discussed above.

Scheme 12 below is a general scheme for the conversion of building blockBB(a) to a boronic ester or ZnCl derivative, followed by doublecross-coupling with building block BB(j) and subsequent deprotection:

In scheme 12, the variables are defined as discussed above.

Scheme 13 below is a general scheme for the double cross-coupling ofbuilding blocks BB(h) or BB(i) with building block BB(a), followed bydeprotection:

In scheme 13, the variables are defined as discussed above.

Scheme 14 below is a general scheme for the double cross-coupling ofbuilding blocks BB(k) or BB(l) with building block BB(a), followed bydeprotection:

In scheme 14, the variables are defined as discussed above.

Scheme 15 below is a general scheme for the double cross-coupling ofbuilding block BB(m), followed by deprotection:

In scheme 15, the variables are defined as discussed above.

Scheme 16 below is a general scheme for the double cross-coupling ofbuilding block BB(n), followed by deprotection:

In scheme 16, the variables are defined as discussed above.

Scheme 17 below is a general scheme for the conversion of building blockBB(m) into a B(OR)₂ or ZnX derivative, followed by double cross-couplingand deprotection:

Scheme 18 below is a general scheme for the conversion of building blockBB(n) into a B(OR)₂ or ZnX derivative, followed by double cross-couplingand deprotection:

Once the desired ligand is formed, it may be combined with a metal atom,ion, compound or other metal precursor compound. For example, in someembodiments, the metal precursors are activated metal precursors, whichrefers to a metal precursor (described below) that has been combined orreacted with an activator (described below) prior to combination orreaction with the ancillary ligand. In some applications, the ligands ofthis invention will be combined with a metal compound or precursor andthe product of such combination is not determined, if a product forms.For example, the ligand may be added to a reaction vessel at the sametime as the metal or metal precursor compound along with the reactants,activators, scavengers, etc. Additionally, the ligand can be modifiedprior to addition to or after the addition of the metal precursor, e.g.through a deprotonation reaction or some other modification.

For formulas I, II, III, IV and V, the metal precursor compounds may becharacterized by the general formula M(L)_(n) where M is a metalselected from the group consisting of groups 3–6 and Lanthanide elementsof the Periodic Table of Elements, more specifically, from group 4 (Hf,Zr and Ti); L is independently selected from the group consisting ofhalide (F, Cl, Br, I), optionally substituted alkyl, alkenyl, alkynyl,heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl, alkoxyl,aryloxyl, silyl, boryl, phosphino, amino, thioxy, alkylthio, arylthio,hydrido, allyl, diene, phosphine, carboxylates, 1,3-dionates, oxalates,carbonates, nitrates, sulphates, ethers, thioethers and combinationsthereof; L may also be ionically bonded to the metal M and for example,L may be a non-coordinated or loosely coordinated or weakly coordinatedanion (e.g., L may be selected from the group consisting of those anionsdescribed below in the conjunction with the activators), see Marks etal., Chem. Rev. 2000, 100, 1391–1434 for a detailed discussion of theseweak interactions; and optionally two or more L groups may be linkedtogether in a ring structure. n is 1, 2, 3, 4, 5, or 6. The metalprecursors may be monomeric, dimeric or higher orders thereof. Specificexamples of suitable titanium, hafnium and zirconium precursors include,but are not limited to TiCl₄, Ti(CH₂Ph)₄, Ti(CH₂CMe₃)₄, Ti(CH₂SiMe₃)₄,Ti(CH₂Ph)₃Cl, Ti(CH₂CMe₃)₃Cl, Ti(CH₂SiMe₃)₃Cl, Ti(CH₂Ph)₂Cl₂,Ti(CH₂CMe₃)₂Cl₂, Ti(CH₂SiMe₃)₂Cl₂, Ti(NMe₂)₄, Ti(NEt₂)₄,Ti(O-isopropyl)₄, and Ti(N(SiMe₃)₂)₂Cl₂; HfC₄, Hf(CH₂Ph)₄, Hf(CH₂CMe₃)₄,Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl, Hf(CH₂SiMe₃)₃Cl,Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂, Hf(NMe₂)₄, Hf(NEt₂)₄,and Hf(N(SiMe₃)₂)₂Cl₂; ZrCl₄, Zr(CH₂Ph)₄, Zr(CH₂CMe₃)₄, Zr(CH₂SiMe₃)₄,Zr(CH₂Ph)₃Cl, Zr(CH₂CMe₃)₃Cl, Zr(CH₂SiMe₃)₃Cl, Zr(CH₂Ph)₂Cl₂,Zr(CH₂CMe₃)₂Cl₂, Zr(CH₂SiMe₃)₂Cl₂, Zr(NMe₂)₄, Zr(NEt₂)₄, Zr(NMe₂)₂Cl₂,Zr(NEt₂)₂Cl₂, and Zr(N(SiMe₃)₂)₂Cl₂. Lewis base adducts of theseexamples are also suitable as metal precursors, for example, ethers,amines, thioethers, phosphines and the like are suitable as Lewis bases.Specific examples include HfCl₄(THF)₂, HfCl₄(SMe₂)₂ andHf(CH₂Ph)₂Cl₂(OEt₂). Activated metal precursors may be ionic orzwitterionic compounds, such as (M(CH₂Ph)₃ ⁺)(B(C₆F₅)₄ ⁻) or (M(CH₂Ph)₃⁺)(PhCH₂B(C₆F₅)₃ ⁻) where M is defined above (and more specifically Hfor Zr). Activated metal precursors or such ionic compounds can beprepared in the manner shown in Pellecchia et al., Organometallics,1994, 13, 298–302; Pellecchia et al., J. Am. Chem. Soc., 1993, 115,1160–1162; Pellecchia et al., Organometallics, 1993, 13, 3773–3775 andBochmann et al., Organometallics, 1993, 12, 633–640, each of which isincorporated herein by reference.

The ligand to metal precursor compound ratio is typically in the rangeof about 0.01:1 to about 100:1, more specifically in the range of about0.1:1 to about 10:1 and even more specifically about 1:1.

This invention, in part, relates to new metal-ligand complexes.Generally, the ligand is mixed with a suitable metal precursor (andoptionally other components, such as activators) prior to orsimultaneously with allowing the mixture to be contacted with thereactants (e.g., monomers). When the ligand is mixed with the metalprecursor compound, a metal-ligand complex may be formed, which may be acatalyst or may need to be activated to be a catalyst.

The metal-ligand complexes of this invention can in general becharacterized in overlapping or alterative descriptions. In oneembodiment, the metal-ligand complexes have dianionic, chelating ligandsthat may occupy up to four coordination sites of the metal atom. Themetal-ligand complexes can also be described as having dianionic ligandsthat form two seven-member metallocycles with the metal atom (countingthe metal atom as one member of the seven member ring). Also, in someembodiments, the metal-ligand complexes can be described as havingdianionic, chelating ligands that use oxygen and/or sulfur as bindingatoms to the metal atom. In still other embodiments, the metal-ligandcomplexes can be described as having non-metallocene ligands that cancoordinate in an approximate C₂ symmetric complex with the metal atom.By approximate C₂ symmetry it is meant that coordination of the ligandwith the metal may still be considered so that the ligand parts occupyfour approximately C₂ symmetric quadrants around the metal centerextending towards the ligands L and approximate means that true symmetrymay not exist due to several factors that effect symmetry, including,for example, the effect of the bridge. In particular, the bulky R²and/or R¹² group the ligand may be approximately C₂ symmetricallyarranged around the metal center. FIGS. 1 a and 1 b demonstrate what ismeant herein by approximate C₂ symmetry. Also, this approximate symmetrycan be determined by proton NMR.

In some embodiments, the metal-ligand complexes of this invention can becharacterized by the general formula:(4,2,O,S)ML_(n),  (VI)where (4,2,O,S) is a dianionic ligand having at least 4 atoms that areeach independently oxygen or sulfur and chelating to the metal M at 4coordination sites through oxygen and/or sulfur atoms with two of thebonds between the oxygen or sulfur atoms and the metal being covelent innature and two of the bonds being dative in nature (i.e., oxygen orsulfur atoms acting as Lewis bases and the metal center acting as aLewis acid); M is a metal selected from the group consisting of groups3–6 and Lanthanide elements of the Periodic Table of Elements, morespecifically, from group 4 (Hf, Zr and Ti); L is independently selectedfrom the group consisting of halide (F, Cl, Br, I), optionallysubstituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl,heteroalkynyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thioxy, alkylthio, arylthio, nitro, hydrido, allyl,diene, phosphine, carboxylates, 1,3-dionates, oxalates, carbonates,nitrates, sulphates, ethers, thioethers and combinations thereof; andoptionally two or more L groups may be linked together in a ringstructure; n′ is 1, 2, 3, or 4.

In other embodiments, the metal-ligand complexes of this invention arethose comprising two seven-member metallocycles formed with bonds fromthe metal atom to at least 2 heteroatoms (e.g., O, S, N, P, Se and thelike). In more specific forms, these metal-ligand complexes comprise twoseven-member metallocycles and even more specifically, there are atleast two seven-member metallocycles that are joined together by atleast one bridging group. In still other embodiments, two, bridgedseven-member metallocycles form a symmetrical complex. Thus for example,the metal-ligand complex below is one embodiment of this invention:

where the complex includes two metallocycles bound by a single bridginggroup.

In still other embodiments, the metal-ligand complexes of this inventionmay be characterized by the general formulas:

wherein each of AR, M, L, B, and n′, are as defined above; and thedotted lines indicate possible binding to the metal atom, provided thatat least two of the dotted lines are covalent bonds. X, X′, X⁴, X⁵, Y²and Y³ are derived from the definitions detailed above in that at leasttwo hydrogen atoms are removed from X, X′, X″, X′″, Y and Y′, in amanner known to those of skill in the art, to form the at least twocovalent bonds between the X and/or Y moieties and the metal. Dependingon the number of covalent bonds, as those of skill in the art candetermine, in some embodiments, X and X′ and Y² and Y³ are the same ordifferent and are independently selected from the group consisting ofoxygen, sulfur, —NR³⁰—, and —PR³⁰—, where R³⁰ is selected from the groupconsisting of hydride, halide, and optionally substituted hydrocarbyl,heteroatom-containing hydrocarbyl, silyl, boryl, alkoxy, aryloxy andcombinations thereof. In other embodiments, Y² and Y³ are the same ordifferent and are independently selected from the group consisting ofoptionally substituted amino, phosphino, hydroxy, alkoxy, aryloxy,thioxy, alkylthio and arylthio. In some embodiments, X⁴ and X⁵ are thesame or different and are independently selected from the groupconsisting of optionally substituted amino, phosphino, hydroxy, alkoxy,aryloxy, thioxy, alkylthio and arylthio, provided that when the bond tothe metal is covalent X⁴ and X⁵ are independently selected from thegroup consisting of oxygen, sulfur, —NR³⁰—, and —PR³⁰—. Note also thatL_(n′) indicates that the metal M is bonded to a number n′ groups of L,as defined above.

In still other embodiments, the metal-ligand complexes of this inventionmay be characterized by the general formula:

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, M, L, n′, B, X, X′, Y² and Y³ are asdefined above and as further explained in connection which structures(VII) and (VIII). The dotted lines indicate possible binding to themetal atom, provided that at least two of the dotted lines are covalentbonds.

In still other embodiments, the metal-ligand complexes of this inventionmay be characterized by the general formula:

wherein R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, M, L, n′, B, X, X′, Y² and Y³ are as defined above are asdefined above and as further explained in connection which structures(VII) and (VIII). The dotted lines indicate possible binding to themetal atom, provided that at least two of the dotted lines are covalentbonds.

In more specific embodiments, the the metal-ligand complexes of thisinvention may be characterized by the general formula:

wherein R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, M, L, n′, B, X, X′, and Y² areas defined above are as defined above and as further explained inconnection which structures (VII) and (VIII). The dotted lines indicatepossible binding to the metal atom, provided that at least two of thedotted lines are covalent bonds. In formula (XI), the metal-ligandcomplex may also have approximate C₂ symmetry that may provide controlof tacticity in the polymerization of propylene to isotacticpolypropylene, when combined with appropriate activator(s).

In addition, specifics for the substituents on the ligands forproduction of the particular polymers discussed above (e.g., isotacticpolypropylene) apply to the metal-ligand complexes. In addition, Lewisbase adducts of the metal-ligand complexes in the above formulas arealso suitable, for example, ethers, amines, thioethers, phosphines andthe like are suitable as Lewis bases. The metal-ligand complexes can beformed by techniques known to those of skill in the art, such ascombinations of metal precursors and ligands under conditions to affordcomplexation. For example, the complexes of this invention can beprepared according to the general scheme shown below:

As shown in Scheme 16, a ligand according to formula (IV) is combinedwith the metal precursor under conditions to cause the removal of atleast 2 leaving group ligands L, which are shown in the scheme ascombining with a hydrogen (H). Other schemes where the leaving groupligand combines with other moieties (e.g., Li) employing other knownroutes for complexation may be used, including for example, reactionswhere the ligand L reacts with other moieties (e.g., where the alkalimetal salt of the ligand is used and the complexation reaction proceedsby salt elimation).

Specific metal-ligand complexes with approximate C₂ symmetry within thescope of the invention include:

The x-ray crystal structure of molecule C5 is shown in FIGS. 1 a and 1b.

The ligands, complexes or catalysts may be supported on organic orinorganic supports. Suitable supports include silicas, aluminas, clays,zeolites, magnesium chloride, polystyrenes, substituted polystyrenes andthe like. Polymeric supports may be cross-linked or not. Similarly, theligands, complexes or catalysts may be supported on similar supportsknown to those of skill in the art. See for example, Hlatky, Chem. Rev.2000, 100, 1347–1376 and Fink et al., Chem. Rev. 2000, 100, 1377–1390,both of which are incorporated herein by reference. In addition, thecatalysts of this invention may be combined with other catalysts in asingle reactor and/or employed in a series of reactors (parallel orserial) in order to form blends of polymer products.

The metal-ligand complexes and compositions are active catalyststypically in combination with a suitable activator, combination ofactivators, activating technique or activating package, although some ofthe ligand-metal complexes may be active without an activator oractivating technique. Broadly, the activator(s) may comprise alumoxanes,Lewis acids, Bronsted acids, compatible non-interfering activators andcombinations of the foregoing. These types of activators have beentaught for use with different compositions or metal complexes in thefollowing references, which are hereby incorporated by reference intheir entirety: U.S. Pat. Nos. 5,599,761, 5,616,664, 5,453,410,5,153,157, 5,064,802, EP-A-277,004 and Marks et al., Chem. Rev. 2000,100, 1391–1434. In particular, ionic or ion forming activators arepreferred.

Suitable ion forming compounds useful as an activator in one embodimentof the present invention comprise a cation that is a Bronsted acidcapable of donating a proton, and an inert, compatible, non-interfering,anion, A⁻. Preferred anions are those containing a single coordinationcomplex comprising a charge-bearing metal or metalloid core.Mechanistically, said anion should be sufficiently labile to bedisplaced by olefinic, diolefinic and unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions that comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion are available commercially.

Specifically such activators may be represented by the following generalformula:(L*-H)_(d) ⁺(A^(d−))wherein L* is a neutral Lewis base; (L*-H)⁺ is a Bronsted acid; A^(d−)is a non-interfering, compatible anion having a charge of d−, and d isan integer from 1 to 3. More specifically A^(d−) corresponds to theformula: (M′³⁺ Q_(h))^(d−) wherein h is an integer from 4 to 6; h−3=d;M′ is an element selected from Group 13 of the Periodic Table of theElements; and Q is independently selected from the group consisting ofhydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, andsubstituted-hydrocarbyl radicals (including halide substitutedhydrocarbyl, such as perhalogenated hydrocarbyl radicals), said Q havingup to 20 carbons. In a more specified embodiment, d is one, i.e., thecounter ion has a single negative charge and corresponds to the formulaA⁻.

Activators comprising boron or aluminum which are particularly useful inthe preparation of catalysts of this invention may be represented by thefollowing general formula:(L*-H)⁺(JQ₄)⁻wherein: L* is as previously defined; J is boron or aluminum; and Q is afluorinated C₁₋₂₀ hydrocarbyl group. Most specifically, Q isindependently selected from the group selected from the group consistingof fluorinated aryl group, especially, a pentafluorophenyl group (i.e.,a C₆F₅ group) or a 3,5-bis(CF₃)₂C₆H₃ group. Illustrative, but notlimiting, examples of boron compounds which may be used as an activatingcocatalyst in the preparation of the improved catalysts of thisinvention are tri-substituted ammonium salts such as: trimethylammoniumtetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylaniliniumtetraphenylborate, N,N-diethylanilinium tetraphenylborate,N,N-dimethylanilinium tetra-(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(secbutyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate andN,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate;dialkyl ammonium salts such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and tri-substituted phosphonium saltssuch as: triphenylphospnonium tetrakis(pentafluorophenyl)borate,tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate;N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;HNMe(C₁₈H₃₇)⁺B(C₆F₅)₄ ⁻; HNPh(C₁₈H₃₇)⁺B(C₆F₅)₄^(− and (()4-nBu-Ph)NH(n-hexyl)₂)⁺B(C₆F₅)₄ ⁻. Specific (L*-H)⁺ cationsare N,N-dimethylanilinium and HNMe(C₁₈H₃₇)⁺. Specified anions aretetrakis(3,5-bis(trifluoromethyl)phenyl)borate andtetrakis(pentafluorophenyl)borate. In some embodiments, the specificactivator is PhNMe₂H⁺B(C₆F₅)₄ ⁻.

Other suitable ion forming activators comprise a salt of a cationicoxidizing agent and a non-interfering, compatible anion represented bythe formula:(Ox^(e+))_(d)(A^(d−))_(e)wherein: Ox^(e+) is a cationic oxidizing agent having a charge of e+; eis an integer from 1 to 3; and A^(d−), and d are as previously defined.Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Specific embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundthat is a salt of a carbenium ion or silyl cation and a non-interfering,compatible anion represented by the formula:©⁺A⁻wherein: ©⁺ is a C₁₋₁₀₀ carbenium ion or silyl cation; and A⁻ is aspreviously defined. A preferred carbenium ion is the trityl cation, i.e.triphenylcarbenium. The silyl cation may be characterized by the formulaZ⁴Z⁵Z⁶Si⁺ cation, where each of Z⁴, Z⁵, and Z⁶ is independently selectedfrom the group consisting of hydride, halide, and optionally substitutedalkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl,aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino,thioxy, alkylthio, arylthio, and combinations thereof. In someembodiments, a specified activator is Ph₃C⁺B(C₆F₅)₄ ⁻.

Other suitable activating cocatalysts comprise a compound that is asalt, which is represented by the formula (A*^(+a))_(b)(Z*J*_(j))^(−c)_(d) wherein A* is a cation of charge +a; Z* is an anion group of from 1to 50, specifically 1 to 30 atoms, not counting hydrogen atoms, furthercontaining two or more Lewis base sites; J* independently eachoccurrence is a Lewis acid coordinated to at least one Lewis base siteof Z*, and optionally two or more such J* groups may be joined togetherin a moiety having multiple Lewis acidic functionality; j is a numberform 2 to 12; and a, b, c, and d are integers from 1 to 3, with theproviso that a×b is equal to c×d. See, WO 99/42467, which isincorporated herein by reference. In other embodiments, the anionportion of these activating cocatalysts may be characterized by theformula ((C₆F₅)₃M″″-LN-M″″(C₆F₅)₃)⁻ where M″″ is boron or aluminum andLN is a linking group, which is specifically selected from the groupconsisting of cyanide, azide, dicyanamide and imidazolide. The cationportion is specifically a quaternary amine. See, e.g., LaPointe, et al.,J. Am. Chem. Soc. 2000, 122, 9560–9561, which is incorporated herein byreference.

In addition, suitable activators include Lewis acids, such as thoseselected from the group consisting of tris(aryl)boranes,tris(substituted aryl)boranes, tris(aryl)alanes, tris(substitutedaryl)alanes, including activators such as tris(pentafluorophenyl)borane.Other useful ion forming Lewis acids include those having two or moreLewis acidic sites, such as those described in WO 99/06413 or Piers, etal. “New Bifunctional Perfluoroaryl Boranes: Synthesis and Reactivity ofthe ortho-Phenylene-Bridged Diboranes 1,2-(B(C₆F₅)₂)₂C₆X₄ (X=H, F)”, J.Am. Chem. Soc., 1999, 121, 3244–3245, both of which are incorporatedherein by reference. Other useful Lewis acids will be evident to thoseof skill in the art. In general, the group of Lewis acid activators iswithin the group of ion forming activators (although exceptions to thisgeneral rule can be found) and the group tends to exclude the group 13reagents listed below. Combinations of ion forming activators may beused.

Other general activators or compounds useful in a polymerizationreaction may be used. These compounds may be activators in somecontexts, but may also serve other functions in the polymerizationsystem, such as alkylating a metal center or scavenging impurities.These compounds are within the general definition of “activator,” butare not considered herein to be ion-forming activators. These compoundsinclude a group 13 reagent that may be characterized by the formulaG¹³R⁵⁰ _(3-p)D_(p) where G¹³ is selected from the group consisting of B,Al, Ga, In and combinations thereof, p is 0, 1 or 2, each R⁵⁰ isindependently selected from the group consisting of hydride, halide, andoptionally substituted alkyl, alkenyl, alkynyl, heteroalkyl,heteroalkenyl, heteroalkynyl, aryl, heteroaryl, and combinationsthereof, and each D is independently selected from the group consistingof halide, hydride, alkoxy, aryloxy, amino, thioxy, alkylthio, arylthio,phosphino and combinations thereof. In other embodiments, the group 13activator is an oligomeric or polymeric alumoxane compound, such asmethylalumoxane and the known modifications thereof. In otherembodiments, a divalent metal reagent may be used that is defined by thegeneral formula M′R⁵⁰ _(2-p′)D_(p′) and p′ is 0 or 1 in this embodimentand R⁵⁰ and D are as defined above. M′ is the metal and is selected fromthe group consisting of Mg, Ca, Sr, Ba, Zn, Cd and combinations thereof.In still other embodiments, an alkali metal reagent may be used that isdefined by the general formula M″R⁵⁰ and in this embodiment R⁵⁰ is asdefined above. M″ is the alkali metal and is selected from the groupconsisting of Li, Na, K, Rb, Cs and combinations thereof. Additionally,hydrogen and/or silanes may be used in the catalytic composition oradded to the polymerization system. Silanes may be characterized by theformula SiR⁵⁰ _(4-q)D_(q) where R⁵⁰ is defined as above, q is 1, 2, 3 or4 and D is as defined above, with the proviso that there is at least oneD that is a hydride.

The molar ratio of metal:activator (whether a composition or complex isemployed as a catalyst) employed specifically ranges from 1:10,000 to100:1, more specifically from 1:5000 to 10:1, most specifically from1:10 to 1:1. In one embodiment of the invention mixtures of the abovecompounds are used, particularly a combination of a group 13 reagent andan ion-forming activator. The molar ratio of group 13 reagent toion-forming activator is specifically from 1:10,000 to 1000:1, morespecifically from 1:5000 to 100:1, most specifically from 1:100 to100:1. In another embodiment, the ion forming activators are combinedwith a group 13 reagent. Another embodiment is a combination of theabove compounds having about 1 equivalent of N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, and 5–30 equivalents of a Group 13reagent.

In other applications, the ligand will be mixed with a suitable metalprecursor compound prior to or simultaneous with allowing the mixture tobe contacted to the reactants. When the ligand is mixed with the metalprecursor compound, a metal-ligand complex may be formed, which may be acatalyst.

The compositions, complexes and/or catalysts of this invention areparticularly effective at polymerizing α-olefins (such as propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and styrene),copolymerizing ethylene with α-olefins (such as propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, and styrene), andcopolymerizing ethylene with 1,1-disubstituted olefins (such asisobutylene). These compositions might also polymerize monomers thathave polar functionalities in homopolymerizations or copolymerizationsand/or homopolymerize 1,1- and 1,2-disubstituted olefins. Also,diolefins in combination with ethylene and/or α-olefins or 1,1- and1,2-disubstituted olefins may be copolymerized.

In general monomers useful herein may be olefinically or unsaturatedmonomers having from 2 to 20 carbon atoms either alone or incombination. Generally, monomers may include olefins, diolefins andunsaturated monomers including ethylene and C₃ to C₂₀ α-olefins such aspropylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene,1-norbornene, styrene and mixtures thereof, additionally,1,1-disubstituted olefins, such as isobutylene, 2-methyl-1-butene,2-methyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-1-hexene,3-trimethylsilyl-2-methyl-1-propene, α-methyl-styrene, either alone orwith other monomers such as ethylene or C₃ to C₂₀ α-olefins and/ordiolefins; additionally 1,2-substituted olefins, such as 2-butene. Theα-olefins listed above may be polymerized in a stereospecific mannere.g. to generate isotactic or syndiotactic or hemiisotacticpolypropylene. Additionally the α-olefins may be polymerized to producea polymer with differing tacticity sequences within the polymer chain,such as polypropylene containing atactic and isotactic sequences withinthe same polymer chain. These definitions are intended to include cyclicolefins. Diolefins generally comprise 1,3-dienes such as (butadiene),substituted 1,3-dienes (such as isoprene) and other substituted1,3-dienes, with the term substituted referring to the same types ofsubstituents referred to above in the definition section. Diolefins alsocomprises 1,5-dienes and other non-conjugated dienes. The styrenemonomers may be unsubstituted or substituted at one or more positions onthe aryl ring. The use of diolefins in this invention is typically inconjunction with another monomer that is not a diolefin. In someembodiments, acetylenically unsaturated monomers may be employed.

More specifically, it has been found that the catalysts of the presentinvention are particularly active for certain monomers, particularly(X-olefins. Thus, the catalysts of the present invention may providehigher comonomer incorporation for copolymers of ethylene andco-monomers having three or more carbon atoms than is currently knownfrom other catalysts. It has been found that particular catalysts of thepresent invention co-polymerize ethylene and styrene (or substitutedstyrenes), forming ethylene-styrene copolymers. Polymers that can beprepared according to the present invention include ethylene copolymerswith at least one C₃–C₂₀ α-olefin, particularly propylene, 1-butene,1-hexene, 4-methyl-1-pentene and 1-octene. The copolymers of ethylenewith at least one C₃–C₂₀ α-olefin comprise from about 0.1 mol. %α-olefin to about 50 mol. % α-olefin, more specifically from about 0.2mol. % α-olefin to about 50 mol. % α-olefin and still more specificallyfrom about 2 mol. % α-olefin to about 30 mol. % higher olefin. Forcertain embodiments of this invention, copolymers include those ofethylene and a comonomer selected from the group consisting ofpropylene, 1-butene, 1-hexene, and 1-octene comprise from about 0.2 toabout 30 mol. % comonomer, more specifically from about 1 to about 20mol. % comonomer, even more specifically from about 2 to about 15 mol. %comonomer and most specifically from about 5 to about 12 mol. %comonomer.

Novel polymers, copolymers or interpolymers may be formed having uniquephysical and/or melt flow properties. Such novel polymers can beemployed alone or with other polymers in a blend to form products thatmay be molded, cast, extruded or spun. End uses for the polymers madewith the catalysts of this invention include films for packaging, trashbags, bottles, containers, foams, coatings, insulating devices andhousehold items. Also, such functionalized polymers are useful as solidsupports for organometallic or chemical synthesis processes.

The α-olefins listed above may be polymerized in a stereoselectivemanner e.g. to generate isotactic or syndiotactic or hemiisotacticpoly-α-olefins. For example, 1-butene may be polymerized into isotacticpoly-1-butene. Additionally the α-olefins may be polymerized to producea polymer with differing tacticity sequences within the polymer chain,such as polypropylene containing atactic and isotactic sequences withinthe same polymer chain. The stereoregularity may be interrupted bystereoerrors, in particular isolated stereoerrors, which is anindication of enantiomorphic side control. Also regioerrors might bepresent in the isotactic polypropylene polymer as it is described in theliterature (see, e.g., Resconi et al., “Selectivity in PropenePolymerization with Metallocene Catalysts,” Chem. Rev. 2000, 100,1253–1345).

More specifically, it has been found that particular catalysts of thepresent invention polymerize propylene to isotactic or crystallinepolypropylene, forming polymers with novel properties. The combinationof isotactic polypropylene properties that are obtained at higherpolymerization temperatures is surprising. In particular, isotacticpolypropylene can be produced having a narrow polydispersity (e.g., lessthan about 3.0 and more specifically less than 2.5) combined with a highmolecular weight (e.g., greater than about 50,000, more specificallygreater than about 100,000 and even more specifically greater than about150,000) in a solution polymerization process at a temperature ofgreater than about 100° C., more specifically greater than 110° C. andeven more specifically greather than 130° C. In addition the isotacticpolypropylene produced by certain embodiments of this invention can beprepared with few or no detectible using ¹³C NMR regio-errors (alsoknown as regio-irrgularities). This is shown in FIG. 2 where theregio-errors are not detectible in certain isotactic polypropylenepolymers prepared as discussed in the examples, using ¹³C NMR methods asdescribed in Rescnoi et al. cited above. It is intended that the ¹³C NMRused herein are typical for polymer characterization.

The isotactic polypropylene polymers formed from these catalysts in asolution polymerization process can be produced at a higher temperaturethan has been described before, such as at a temperature of greater thanabout 100° C., more specifically greater than 110° C. and even morespecifically greather than 130° C. The polymerization conditions aredescribed herein, producing isotactic polypropylene with a crystallinityindex of between about 0.35 and about 0.95, more specifically betweenabout 0.65 and 0.95 and in some embodiments specifically above about0.8, under the polymerization conditions employed. The crystallinityindex is determined using FTIR as is known to those of skill in the artand calibrated based on a relative scale. In one embodiment, thecrystallinity index value can be determined using commercially availableFTIR equipment (such as a Bruker Equinox 55 with an IR Scope II inreflection mode using Pike MappIR software). The crystallinity index isobtained from the ratio of band heights at 995 cm⁻¹ and 972 cm⁻¹.Atactic polypropylene has a ratio of band heights or crystallinity indexof 0.2. Greater than 98% isotactic polypropylene has a crystallinityindex ratio of greater than 0.95. Generally, the amount of error incrystallinity index measurements is ±0.05. Polymer blends of variouscompositions show a linear relationship between % isotacticity andcrystallinity index. See, for example, J. P. Luongo, J. Appl. Polym.Sci., 3 (1960) 302–309 and T. Sundell, H. Fagerholm, H. Crozier, Polymer37 (1996) 3227–3231, each of which is incorporated herein by reference.

As those of skill in the art will recognize, isotacticity can also berepresented by percent pentads (% mmmm) as determined by ¹³C NMRspectroscopy. Proton decoupled ¹³C NMR spectroscopy can be performedusing commercially available equipment (such as a Bruker 300 MHz at 100°C. probe temperature) to determine the degree of tacticity as % mmmmpentads (for assignment of ¹³C signals see the review Brintzinger H. H.et al., Angew. Chem. Int. Ed. Eng. 1995, 34, 1143, which is incorporatedherein by reference; and Resconi, Chem. Rev. 2000, 100, 1253–1345 andGibson, et al., Chem Rev. 2003, 103, 283–315). For example, a 15–30 mgpolymer sample is dissolved in a 1:1 mixture of C₂D₂Cl₄ and C₂Cl₄ byheating the sample to ca. 100° C. The % mmmm is determined by the ratioof peak integral from 23.5 to 21.5 ppm and peak integral 23.5 to 19 ppm(in the absence of significant chain end regio-irregularity signals inthis region). Proton decoupled ¹³C NMR spectroscopy can be alsoperformed to determine the frequency of and nature of stereoerrors andregioerrors.

In addition, the melting point of the crystalline polypropylene isgenerally in the range of from about 115° C. to about 165° C., morespecifically between about 120° C. and 155° C., and in some embodimentsspecifically above about 135° C. Melting points are determined bydifferential scanning calorimetry, as is known in the art (see also theexample section, herein).

Novel polymers, copolymers or interpolymers may be formed having uniquephysical and/or melt flow properties. Polymers that can be preparedaccording to the present invention include propylene copolymers with atleast one C₄–C₂₀ α-olefin, particularly 1-butene, 1-hexene,4-methyl-1-pentene and 1-octene. The copolymers of propylene with atleast one C₄–C₂₀ α-olefin comprise from about 0.1 wt. % higher olefin toabout 60 wt. % higher olefin, more specifically from about 0.2 wt. %higher olefin to about 50 wt. % higher olefin and still morespecifically from about 2 wt. % higher olefin to about 30 wt. % higherolefin. For certain embodiments of this invention, crystallinecopolymers include those of propylene and a comonomer selected from thegroup consisting of ethylene, 1-butene, 1-hexene, and 1-octene comprisefrom about 0.2 to about 30 wt. % comonomer, more specifically from about1 to about 20 wt. % comonomer, even more specifically from about 2 toabout 15 wt. % comonomer and most specifically from about 5 to about 12wt. % comonomer.

The novel polymers (such as isotactic polypropylene) disclosed hereincan be employed alone or with other natural or synthetic polymers in ablend. Such other natural or synthetic polymers can be polyethylene(including linear low density polyethylene, low density polyethylene,high density polyethylene, etc.), atactic polypropylene, nylon, EPDM,ethylene-propylene elastomer copolymers, polystyrene (includingsyndiotactic polystryene), ethylene-styrene copolymers and terpolymersof ethylene-styrene and other C₃–C₂₀ olefins (such as propylene).

Melt flow rate (MRF) for polypropylene and copolymer of propylene andone or more C₄–C₂₀ α-olefins is measured according to ASTM D-1238,condition L (2.16 kg, 230° C.). In some embodiments of this invention,the MFR is in the range of 0.005–1,000, more specifically 0.01–500 andeven more specifically 0.1–100. Flex modulus for polypropylene andcopolymer of propylene and one or more C₄–C₂₀ α-olefins is measuredaccording to ASTM D-790. In some embodiments of this invention, the flexmodulus ranges from 20,000–400,000 psi, more specifically from20,000–300,000 psi and even more specifically from 100,000–200,000 psi.Notch izod impact for polypropylene and copolymer of propylene and oneor more C₄–C₂₀ α-olefins is measured according to ASTM D-256A. In someembodiments of this invention, the notch izod impact ranges from 0.1 tono break in ft-lbs/in.

The novel polypropylene and copolymer of propylene and one or moreC₄–C₂₀ α-olefins disclosed in the present invention are useful for awide variety of applications, including films (such as blown and castfilm, clarity film and multi-layer films), thermoforming (such as cups,plates, trays and containers), injection moulding, blow-moulding, foams(such as structural foams), pipe (such as potable water pipe and highpressure pipe), automotive parts, and other applications that will beevident to those of skill in the art.

Melt strength (measured in cN) and melt drawability (measured in mm/s)tests are conducted by pulling (“taking-up”) strands of the moltenpolymers or blends at constant acceleration until breakage occurs. Anexperimental set-up comprises a capillary rheometer and a Rheotensapparatus as a take-up device. The molten strands are drawn uniaxiallyto a set of accelerating nips located 100 mm below the die. The forcerequired to uniaxially extend the strands is recorded as a function ofthe take-up velocity or the nip rolls. In the case of polymer meltsexhibiting draw resonance (indicated by the onset of a periodicoscillation of increasing amplitude in the measured force profile), themaximum force and wheel velocity before the onset of draw resonance aretaken as the melt strength and melt drawability, respectively. In theabsence of draw resonance, the maximum force attained during testing isdefined as the melt strength and the velocity at which breakage occursis defined as the melt drawability. These tests are typically run underthe following conditions:

Mass flow rate 1.35 grams/min Temperature 190° C. Equilibration time at190° C. 10 minutes Die 20:1 (with entrance angle of approximately 45degrees) Capillary length 41.9 mm Capillary diameter 2.1 mm Pistondiameter 9.54 mm Piston velocity 0.423 mm/s Shear rate 33.0 s⁻¹Draw-down distance (die exit 100 mm to take-up sheels) Coolingconditions Ambient air Acceleration 2.4 mm/s²

For some aspects of the present invention the novel polymers are usefulto produce foams having improved properties. For foams and otherapplications requiring melt strength, the MFR is typically in the rangeof 0.1–10, more specifically in the range of 0.3–3 and most specificallyin the range of 0.5–2. The melt strength is typically greater than 5 cN,more specifically greater than 9 cN and most specifically greater than12 cN. The drawability is typically greater than 15 mm/sec, morespecifically greater than 25 mm/sec and most specifically greater than35 mm/sec.

In some aspects of the present invention, the novel polymers disclosedherein are useful for a wide variety of applications where certainoptical properties are beneficial. Gloss is measured according to ASTMD-1746. Haze is measured according to ASTM D-1003 and clarity ismeasured according to ASTM D-2457. The novel polymers disclosed hereinin some aspects are films having haze of less than 10%. In additionfilms having clarity of greater than 91% may be beneficially obtained.

Polymerization is carried out under polymerization conditions, includingtemperatures of from −100° C. to 300° C. and pressures from atmosphericto 3000 atmospheres. Suspension, solution, slurry, gas phase orhigh-pressure polymerization processes may be employed with thecatalysts and compounds of this invention. Such processes can be run ina batch, semi-batch or continuous mode. Examples of such processes arewell known in the art. A support for the catalyst may be employed, whichmay be inorganic (such as alumina, magnesium chloride or silica) ororganic (such as a polymer or cross-linked polymer). Methods for thepreparation of supported catalysts are known in the art. Slurry,suspension, gas phase and high-pressure processes as known to thoseskilled in the art may also be used with supported catalysts of theinvention.

Other additives that are useful in a polymerization reaction may beemployed, such as scavengers, promoters, modifiers and/or chain transferagents, such as hydrogen, aluminum alkyls and/or silanes.

As discussed herein, catalytic performance can be determined a number ofdifferent ways, as those of skill in the art will appreciate. Catalyticperformance can be determined by the yield of polymer obtained per moleof metal complex, which in some contexts may be considered to beactivity. The examples provide data for these comparisons.

Another measure of catalyst polymerization performance is co-monomerincorporation. As is well known in the art, many ethylene copolymers areprepared using ethylene and at least one other monomer. These copolymersor higher order polymers in some applications require higher amounts ofadditional co-monomer(s) than have been practical with known catalysts.Since ethylene tends to be the most reactive monomer, obtaining higherco-monomer incorporations is a benefit that is examined forpolymerization catalysts. Two useful co-monomers are 1-octene andstyrene. This invention offers the possibility of higher incorporationof co-monomers such as 1-octene and styrene.

As stated herein, a solution process is specified for certain benefits,with the solution process being run at a temperature above 90° C., morespecifically at a temperature above 100° C., further more specificallyat a temperature above 110° C. and even further more specifically at atemperature above 130° C. Suitable solvents for polymerization arenon-coordinating, inert liquids. Examples include straight andbranched-chain hydrocarbons such as isobutane, butane, pentane,isopentane, hexane, isohexane, heptane, octane, Isopar-E® and mixturesthereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; perhalogenated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, chlorobenzene, and aromatic and alkyl substituted aromaticcompounds such as benzene, toluene, mesitylene, and xylene. Suitablesolvents also include liquid olefins which may act as monomers orcomonomers including ethylene, propylene, 1-butene, butadiene,cyclopentene, 1-hexene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, isobutylene,styrene, divinylbenzene, allylbenzene, and vinyltoluene (including allisomers alone or in admixture). Mixtures of the foregoing are alsosuitable.

In some embodiments, a solution process is specified for crystallinepolypropylene production. The solution process to prepare isotacticpolypropylene comprises adding a catalyst and propylene monomer to areactor and subjecting the contents to polymerization conditions.

The ligands, metal-ligand complexes and compositions of this inventioncan be prepared and tested for catalytic activity in one or more of theabove reactions in a combinatorial fashion. Combinatorial chemistrygenerally involves the parallel or rapid serial synthesis and/orscreening or characterization of compounds and compositions of matter.U.S. Pat. Nos. 5,985,356, 6,030,917 and WO 98/03521, all of which areincorporated herein by reference, generally disclose combinatorialmethods. In this regard, the ligands, metal-ligand complexes orcompositions may be prepared and/or tested in rapid serial and/orparallel fashion, e.g., in an array format. When prepared in an arrayformat, ligands, metal-ligand complexes or compositions may be take theform of an array comprising a plurality of compounds wherein eachcompound can be characterized by any of the above general formulas(i.e., I, II, III, etc.). An array of ligands may be synthesized usingthe procedures outlined previously. The array may also be of metalprecursor compounds, the metal-ligand complexes or compositionscharacterized by the previously described formulae and/or description.Typically, each member of the array will have differences so that, forexample, a ligand or activator or metal precursor or R group in a firstregion of the array may be different than the ligand or activator ormetal precursor or R group in a second region of the array. Othervariables may also differ from region to region in the array.

In such a combinatorial array, typically each of the plurality ofcompositions or complexes has a different composition or stoichiometry,and typically each composition or complex is at a selected region on asubstrate such that each compound is isolated from the othercompositions or complexes. This isolation can take many forms, typicallydepending on the substrate used. If a flat substrate is used, there maysimply be sufficient space between regions so that there cannot beinterdiffusion between compositions or complexes. As another example,the substrate can be a microtiter or similar plate having wells so thateach composition or complex is in a region separated from othercompounds in other regions by a physical barrier. The array may alsocomprise a parallel reactor or testing chamber.

The array typically comprises at least 8 compounds, complexes orcompositions each having a different chemical formula, meaning thatthere must be at least one different atom or bond differentiating themembers in the array or different ratios of the components referred toherein (with components referring to ligands, metal precursors,activators, group 13 reagents, solvents, monomers, supports, etc.). Inother embodiments, there are at least 20 compounds, complexes orcompositions on or in the substrate each having a different chemicalformula. In still other embodiments, there are at least 40 or 90 or 124compounds, complexes or compositions on or in the substrate each havinga different chemical formula. Because of the manner of formingcombinatorial arrays, it may be that each compound, complex orcomposition may not be worked-up, purified or isolated, and for example,may contain reaction by-products or impurities or unreacted startingmaterials.

The catalytic performance of the compounds, complexes or compositions ofthis invention can be tested in a combinatorial or high throughputfashion. Polymerizations can also be performed in a combinatorialfashion, see, e.g., U.S. Pat. Nos. 6,306,658, 6,508,984 and WO 01/98371,each of which is herein incorporated by reference.

EXAMPLES

General: All reactions were performed under a purified argon or nitrogenatmosphere in a Braun or Vacuum Atmospheres glove box. All solvents usedwere anhydrous, de-oxygenated and purified according to knowntechniques. All ligands and metal precursors were prepared according toprocedures known to those of skill in the art, e.g., under inertatmosphere conditions, etc. Ethylene/styrene and ethylene/1-octenecopolymerizations and propylene polymerizations were carried out in aparallel pressure reactor, which is fully described in U.S. Pat. Nos.6,306,658, 6,455,316 and 6,489,168, and in U.S. application Ser. No.09/177,170, filed Oct. 22, 1998, and WO 00/09255, each of which isincorporated herein by reference.

High temperature Size Exclusion Chromatography was performed using anautomated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816,6,491,823, 6,475,391, 6,461,515, 6,436,292, 6,406,632, 6,175,409,6,454,947, 6,260,407, and 6,294,388 each of which is incorporated hereinby reference. In the current apparatus, a series of two 30 cm×7.5 mmlinear columns, with one column containing PLgel 10 um, MixB and theother column containing PLgel 5 um, MixC (available from Polymer Labs).The GPC system was calibrated using narrow polystyrene standards. Thesystem was operated at a eluent flow rate of 1.5 mL/min and an oventemperature of 160° C. o-dichlorobenzene was used as the eluent. Thepolymer samples were dissolved 1,2,4-trichlorobenzene at a concentrationof about 1 mg/mL. Between 40 μL and 200 μL of a polymer solution wereinjected into the system. The concentration of the polymer in the eluentwas monitored using an evaporative light scattering detector. All of themolecular weight results obtained are relative to linear polystyrenestandards.

The ratio of 1-octene to ethylene incorporated in the ethylene-octenecopolymer products was determined by Raman spectroscopy. All spectrawere obtained using a Bruker Equinox 055 FRA 106/S FT-Raman Spectrometer(Raman back scattering) with a 4 min acquisition time, a laser power of500 mW, and spectral resolution of 4 cm⁻¹. Analysis was performed usingOPUS NT software package by measuring the absorbance of the peaks at2953, 2955, and 2957 cm⁻¹ (for the asymmetric CH₃ stretch) and the peakmaximum between 2844 and 2854 cm⁻¹ (for the symmetric CH₂ stretch). Theabsorbance of the baseline at 3200 cm⁻¹ was then subtracted from thesevalues and the ratio of the peak heights was determined. Mol % 1-octenevalues determined from x=A2953/A2850 ratio where Mol%=1233.2×2−160.26x+8.2296. This method was calibrated using a set ofethylene/1-octene copolymers with a range of known wt. % 1-octenecontent.

Crystallinity in polypropylene was determined by FTIR spectroscopy. FTIRspectra of thin films deposited from solution onto gold coated Si wafersare acquired at 4 cm⁻¹ resolution and with 16 scans inreflection-absorption mode on a Bruker Equinox 55 FTIR spectrometerequipped with a Pike MappIR accessory. The height ratio of two bands at995 cm⁻¹ (C—H bending and CH₃ rocking mode from regular crystallineisotactic helices) and 972 cm⁻¹ (coupled C—C stretching and CH₃ rockingmode, independent of crystallinity) is determined as a measure ofisotacticity (as known in the art, see, e.g., J. P. Luongo, J. Appl.Polym. Sci 3 (1960) 302–309, and T. Sundell, H. Fagerholm, H. Crozier,Polymer 37 (1996) 3227–3231, each of which is incorporated herein byreference). For blends of atactic and isotactic polypropylene (PP) with0–70% isotactic PP, the IR ratio is proportional to the percentage ofisotactic PP. For greater than 98% isotactic PP the ratio is greaterthan 0.95, for amorphous PP the ratio is 0.2.

The ratio of styrene to ethylene incorporated in the polymer products,represented as the mol % of styrene incorporated in the polymer (mol %styrene) was determined using FTIR spectroscopy. The IR spectra (16scans at 4 cm⁻¹ resolution) analyzed by Partial Least Squares (PLS)analysis with PLSplus/IQ V3.04 for GRAMS/32 (Galactic Industries)software, using the following training set for calibration.

Training Set

The analysis based on a training set consisting of 180 spectra of blendsof ethylene-styrene copolymers with known styrene incorporation, andatactic homo-polystyrene. The 16 known copolymers had between 1 and 47mol % incorporated styrene. The atactic homo-polystyrene content in theblends ranged from 0 to 90% of the total styrene content of the blend.Most blends are prepared from copolymers with up to 20 mol %incorporation. Multiple spectra per blend were included in the trainingset.

Preprocessing of the Spectra

Mean centering; linear baseline correction based on average absorbancesat 2074 cm⁻¹–2218 cm⁻¹ and 3224 cm⁻¹–3465 cm⁻¹; thickness correctionbased on band area from 1483 cm⁻¹ to 1504 cm⁻¹ with baseline from 1389cm⁻¹–1413 cm⁻¹ to 1518 cm⁻¹–1527 cm⁻¹.

Analysis

PLS-1 algorithm; spectral regions 499 cm⁻¹ to 2033 cm⁻¹ and 3577 cm⁻¹ to4495 cm⁻¹. Prediction of number ratios of atactic homo-polystyrene tototal styrene (∝ % atactic homo-polystyrene to total styrene) with 10factors and ethylene to total styrene (∝ mol % total styrene) with 7factors and calculation of mol % incorporated styrene from these 2numbers.

FTIR method for determining mol % total styrene in product: FTIR wasperformed on a Bruker Equinox 55+IR Scope II in reflection mode using aPike MappIR accessory with 16 scans. The ratio of total styrene toethylene was obtained from the ratio of band heights at 4330 cm⁻¹ and1602 cm⁻¹. This method was calibrated using a set of ethylene-styrenecopolymers with a range of known styrene content. The total styrenecontent of the polymer products (mol % total styrene), includes both thestyrene incorporated in the ethylene-styrene copolymer and anybackground homopolystyrene (PS) in the product sample. For theethylene-styrene copolymerization conditions employed, thehomopolystyrene background level is typically less than 3.5 wt % (1 mol%).

Differential Scanning Calorimetry (DSC) measurements were performed on aTA instrument DSC 2920 to determine the melting point of polymers. Thesample was equilibrated at 2000 and held for 4 minutes. The sample wascooled to −50° C. with a rate of 10° C./min and held at −50° C. for 4minutes. Then, the sample was heated to 200° C. at a rate of 10° C./minand data were collected during that heating period.

List of Abbreviations used in this section include: Me=methyl, Et=ethyl,Bn or Bz=benzyl, Ac=CH₃CO, EA=ethyl acetate,Ts=tosyl=para-toluenesulfonyl, THP=tetrahydropyran,dppf=1,1′-bis(diphenylphosphino)ferrocene, MOM=methoxymethyl=CH₃OCH₂—,DMF=dimethylformamide

The ligands in these examples are prepared according to the generalschemes described above and shown below, where “building blocks” arefirst prepared and then coupled together.

Part A: Synthesis of Building Blocks

Part 1: Synthesis of Substituted 2-Bromophenols and 2-BromophenyletherBuilding Blocks:

Example 1 Scheme A1

Building Blocks BB1 and BB2

Step 1: CuI-Catalyzed Cross-coupling:

A solution of the protected 2-bromophenol (4.6 mmol) and carbazole (5.5mmol) in dioxane (8 mL) was degassed with argon. CuI (0.215 mmol, 5%),racemic trans-1,2-diaminocyclohexane (0.86 mmol, 20%), and K₃PO₄ (8mmol) were added and the resulting mixture was stirred at 100° C. for 16h. After filtration, the solvent was removed and crude product waspurified by flash chromatography to give 4.04 mmol of the product (88%yield).

Step 2: Cleavage of the Methyl Ether:

To a solution of the carbazole methyl ether in dry CH₂Cl₂ were added twoequivalents of BBr₃ (1 M solution in CH₂Cl₂) and the resulting solutionwas stirred for 5 hours (TLC control). Water was added, the resultingmixture was extracted with ethyl acetate, and the organic layer wasdried over Na₂SO₄. The crude product was purified by flashchromatography.

Step 3: Bromination:

To a solution of the carbazole phenol (4.3 mmol) and NEt₃ (4.3 mmol) inCH₂Cl₂ (10 ml) was added dropwise a solution of NBS (N-bromosuccinimide,4.8 mmol) in CH₂Cl₂ (30 mL). The resulting solution was stirred for 30min and then quenched with 2N HCl (5 mL). Water (30 mL) was added, themixture was extracted with CH₂Cl₂, and the organic layer was dried overNa₂SO₄. The crude product was purified by flash chromatography to give1.8 mmol of the product (43% yield) (JZ-1009-31). ¹H NMR (300 MHz,CDCl₃): 8.15 (d, 2H), 7.11–7.52 (m, 8H), 5.35 (s, 1H), 2.34 (s, 3H).(GC-MS available)

Step 4: Protection of Phenol as Methyl Ether (BB1) or Benzyl Ether(BB2):

A mixture of a phenol building block (1 equiv.), MeI or BnBr (1.5equiv.) and K₂CO₃ (2 equiv.) in acetone (ca. 0.5 mmol/ml) was stirred at60° C. for 2–4 hours. After addition of CH₂Cl₂ and filtration, thesolvent was removed in vacu and the crude product was dried in a vacuumoven.

Some additional 2-bromophenol building blocks synthesized in a mannersimilar to that described in Scheme A1(a):

Synthesis of 2-Bromophenol Building Block BB5

Step 1: n-BuLi (22.5 mmol, from a 1.6 M solution in hexanes, 14 mL) wasadded slowly to a solution of the aryl bromide (21.44 mmol, 5 g) in THF(50 mL, anhydrous) at −78° C. under an atmosphere of argon. Afterstirring for 30 min at that temperature, triisopropyl borate (25.7 mmol,6 mL) was added slowly and the temperature was allowed to come to roomtemperature (30 min). After stirring for another 30 min, the solvent wasremoved and the crude boronic acid was used without furtherpurification.

Step 2: A mixture of the protected 2-bromophenol (methyl ether, 3.38 g,16.8 mmol), the boronic acid (22.5 mmol), Na₂CO₃ (9 mL of a 2 M solutionin water, 18 mmol) and dimethoxy ethane (100 mL) was degassed withargon. Pd(PPh₃)₃ (485 mg, 0.42 mmol, 2.5%) was added and the resultingmixture was stirred at 85° C. for 16 h under argon. Ethyl acetate (30mL) was added and the mixture was dried over Na₂SO₄. After filtration,the solvent was removed and the crude product was purified by flashchromatography (Ethylacetate/hexane=1/10) to give 1.7 g of thecross-coupling product (6 mmol, 28% yield). After cleavage of the methylether with BBr₃ in CH₂Cl₂ and bromination with NBS as shown in SchemeA1(a), the crude product was purified to yield 1.4 g of the buildingblock BB5 (4.13 mmol, 68%). (characterized by GC-MS, ¹H NMR).

Some additional 2-bromophenol building blocks (BB6 to BB12) synthesizedin a manner similar to that described above in connection with SchemeA1(b):

2-bromophenol building blocks synthesized in a manner similar to thatdescribed above for Scheme A1(c) (only bromination and deprotection):

Example 2 Scheme A2: Synthesis of Substituted 2-Bromophenyl-BenzylEthers via 2,6-dibromo-4-methyl-phenyl benzyl ether

Synthesis of Building Block BB16

n-BuLi (4 mmol, from a 1.6 M solution in hexanes, 2.5 mL) was addedslowly to a solution of the aryl bromide (3.72 mmol, 1 g) in THF (10 mL,anhydrous) at −78° C. under an atmosphere of argon. After stirring for10 min at that temperature, triisopropyl borate (4.3 mmol, 988 μL) wasadded slowly and the temperature was allowed to come to room temperature(30 min). After stirring for another 30 min, the solvent was removed andthe crude aryl boronic acid was used without further purification. Amixture of the protected 2,6-dibromophenol (benzyl ether, 1.07 g, 3mmol), the boronic acid (3.72 mmol), Na₂CO₃ (2.5 mL of a 2 M solution inwater, 5 mmol) and dimethoxy ethane (15 mL) was degassed with argon.Pd(PPh₃)₃ (170 mg, 0.15 mmol, 5%) was added and the resulting mixturewas stirred at 85° C. for 16 h under argon. Ethyl acetate (30 mL) wasadded and the mixture was dried over Na₂SO₄. After filtration, thesolvent was removed and the crude product was purified by flashchromatography (Ethylacetate/hexane=1/10) to give 1.143 g of the productBB16 (2.46 mmol, 82% yield).

Some additional building blocks synthesized in a manner similar to thatdescribed above in connection with Scheme A2(a):

Part 2: Synthesis of Boronic Ester Building Blocks

Example 3 Scheme A3

Introduction of the THP (tetrahydropyran) protection group—A solution of2-bromophenol (25 g, 145 mmol), dihydropyran (22.3 g, 264 mmol) andpyridinium p-toluenesulfonate (“PPTs”, 3.3 g, 13 mmol) in methylenechloride (100 mL) was stirred for 16 h at room temperature. Theresulting solution was washed with aq. NH₄C₁, H₂O and brine, and driedover Na₂SO₄. After removal of the solvent, the THP-protected2-bromophenol was isolated as a yellow oil (35 g, 137 mmol, 95%).

Formation of the boronic ester—n-BuLi (1.1 mmol, from a 1.6 M solutionin hexanes) was added slowly to a solution of the THP-protected2-bromophenol (1 mmol) in THF (5 mL, anhydrous) at −78° C. under anatmosphere of argon. After stirring for 10 min at that temperature,triisopropyl borate was added slowly and the temperature was allowed tocome to room temperature (30 min). After stirring for another 30 min,the solvent was removed and the crude THP-protected boronic ester (BB20)was used without further purification.

Some additional building blocks synthesized in a manner similar to thatdescribed above in connection with Scheme A3:

Example 4 Scheme A4

A solution of bromobenzenethiol (25 g, 132 mmol), dihydropyran (22.3 g,264 mmol) and pyridinium p-toluenesulfonate (“PPTs”, 3.3 g, 13 mmol) inmethylene chloride (100 mL) was stirred for 16 h at room temperature.The resulting solution was washed with aq. NH₄Cl, H₂O and brine, anddried over Na₂SO₄. After removal of the solvent, the THP-protected2-bromothiophenol was isolated as a yellow oil (34 g, 125 mmol, 95%).The corresponding THP-protected boronic ester (BB21) was preparedaccording to standard methods described above.

Part 3: Synthesis of (O,O)- and (O,S)-Bridged Building Blocks

Example 5 (O,O)-Bridged Building Block BB22

A mixture of bromophenol (40 mmol, 4.64 mL), 1,3-dibromopropane (20mmol, 2.03 mL) and Cs₂CO₃ (50 mmol, 16.3 g) in acetone (100 mL) wasstirred at 60° C. for 16 hours. After addition of CH₂Cl₂ and filtration,the solvent was removed in vacu and the crude product was dried in avacuum oven to give 5.77 g of BB22 (75%). (characterized by GC-MS, ¹HNMR)

Example 6 (O,S)-Bridged Building Block BB23

A mixture of bromophenol (4.62 mmol, 800 mg), 1,4-dibromobutane (20mmol, 4.32 g) and K₂CO₃ (10 mmol, 1.38 g) in acetone (10 mL) was stirredat 60° C. for 1 hour. After addition of CH₂Cl₂ and filtration, thesolvent was removed and the crude product was purified by flashchromatography (Ethylacetate/hexane=1/10) to give 1.278 g of the product(4.15 mmol, 90% yield). Bromothiophenol (4.15 mmol, 784 mg), K₂CO₃ (10mmol, 1.38 g) and acetone (10 mL) were added and the resulting mixturewas stirred at 60° C. for 2 hours. After addition of CH₂Cl₂ andfiltration, the solvent was removed to give 1.693 g of the product BB23(4.07 mmol, 88% yield). (characterized by GC-MS, ¹H NMR)

Example 7 Synthesis of (O,O)- and (O,S)-Bridged Bis Aryl Boronic Esters

Building Block BB24:

A mixture of the (O,O)-bridged bis(arylbromide) BB22 (397 mg, 1.03mmol), the boronic ester (574 mg, 2.26 mmol), KOAc (607 mg, 6.16 mmol)and toluene (15 mL) was degassed with argon. PdCl₂(dppf) (50 mg, 0.06mmol) was added and the resulting mixture was stirred at 85° C. for 16 hunder argon. After filtration, the solvent was removed and the crudeproduct was purified by flash chromatography (CH₂Cl₂/hexane=10/1, add 1%of NEt₃) to give 240 mg of the product (O,O)-bridged bis(aryl boronicester) BB24 (0.5 mmol, 50% yield).

Building Block BB25:

A mixture of the (O,S)-bridged bis(arylbromide) BB23 (416 mg, 1 mmol),the boronic ester (559 mg, 2.2 mmol), KOAc (588 mg, 6 mmol) and toluene(15 mL) was degassed with argon. PdCl₂(dppf) (50 mg, 0.06 mmol) wasadded and the resulting mixture was stirred at 85° C. for 16 h underargon. After filtration, the solvent was removed and the crude productwas purified by flash chromatography (CH₂Cl₂/hexane=10/1, add 1% ofNEt₃) to give 110 mg of the product (O,S)-bridged bis(aryl boronicester) BB25 (0.5 mmol, 50% yield).

Part B: Synthesis of (O,O)-Bridged Bis(Biphenylphenol) Ligands:

Detailed Example of a Ligand Synthesized According to Scheme B1:

Example 8 Building Block BB26: Procedure B1 Step 1

A mixture of the benzyl ether protected 2-bromophenol (BB14, 670 mg, 1.7mmol), the in situ formed O-THP protected ary boronic acid (BB20, 750mg, 2.5 mmol), Na₂CO₃ (1.5 mL of a 2 M solution in water, 3 mmol) anddimethoxy ethane (10 mL) was degassed with argon. Pd(PPh₃)₃ (230 mg, 0.2mmol, 10%) was added and the resulting mixture was stirred at 85° C. for16 h under argon. Ethyl acetate (30 mL) was added and the mixture wasdried over Na₂SO₄. After filtration, the solvent was removed and the THPether was cleaved in the presence of HCl (0.2 mL), EA (1 mL), and MeOH(1 mL). The crude product was purified by flash chromatography(Ethylacetate/hexane=1/10) to give 638 mg of the product BB26 (1.56mmol, 92% yield). ¹H NMR (300 MHz, CDCl₃): 7.64 (d br, J=7 Hz, 2H),7.35–7.52 (m, 7H), 7.05–7.25 (m, 5H), 7.72 (d br, J=7 Hz, 2H), 4.27 (s,2H), 1.40 (s, 9H).

Example 9 Ligand LL1: Procedure B1 Step 2

A mixture of the phenol building block (BB26) (418 mg, 1.01 mmol),1,4-dibromobutane (109 mg, 0.5 mmol), and K₂CO₃ (260 mgs, 2 mmol) inacetone (5 mL) was stirred at 60° C. for 16 hours. After filtration, thesolvent was removed and the crude product was dissolved in ethyl acetate(2 mL) and EtOH (2 mL). Pd (100 mg, 10% on activated carbon) was addedand the suspension was stirred under an atmosphere of hydrogen for 16 hat room temperature and at 50° C. for 3 hours. After filtration andremoval of the solvent, the crude product was purified by flashchromatography (Ethylacetate/hexane=1/10) to yield 205 mg of the finalproduct LL1 as a white solid (0.297 mmol, 59%). ¹H NMR (300 MHz, CDCl₃):7.52 (d br, J=7 Hz, 4H), 7.36 (t br, J=7 Hz, 4H), 7.26–7.34 (m, 8H),7.18 (d, J=2.5 Hz, 2H), 7.09 (t, J=7.5 Hz, 2H), 6.89 (d, J=8 Hz, 2H),6.00 (s, 2H), 3.94 (br, 4H), 1.78 (br, 4H), 1.32 (s, 18H).

Some additional ligands synthesized in a method similar to that justdescribed according to Scheme B1 chosen to exemplify some variations inthe synthetic method:

Example 10 Building Block BB27

According to Scheme B 1 and General Procedure B 1 Step 1, the in situgenerated O-THP boronic acid BB20 (0.7 mmol), the protected2-bromophenol building block BB16 (0.5 mmol, 232 mg), Na₂CO₃ (0.5 mL ofa 2 M solution in water, 1 mmol) and dimethoxy ethane (7 mL) werereacted in the presence of Pd(PPh₃)₃ (80 mg, 0.07 mmol) at 85° C. for 16h. After cleavage of the THP ether and purification, 128 mg of theproduct BB27 was obtained (0.268 mmol, 54% yield). ¹H NMR (300 MHz,CDCl₃): 7.52 (t, J=2 Hz, 1H), 7.35–7.42 (m, 5H), 7.22–7.30 (m, 2H),7.05–7.20 (5H), 6.65 (dbr, J=7 Hz, 2H), 4.29 (s, 2H), 2.47 (s, 3H), 1.34(s, 18H).

Example 11 Ligand LL2

According to Scheme B1 and General Procedure B1 Step 2, a mixture of thephenol building block BB27 (128 mg, 0.268 mmol),propane-1,3-diol-di-p-tosylate (51 mg, 0.134 mmol), and Cs₂CO₃ (163 mgs,0.5 mmol) in acetone (2 mL) was stirred at 60° C. for 16 hours. Afterstirring the benzyl ether under an atmosphere of H₂ (500 psi) in thepresence of Pd/C (50 mg, 5%, Aldrich) in ethyl acetate (1 mL), EtOH (1mL) and AcOH (1 drop) at 50° C. for 2 h, the product was purified byflash chromatography to give 54 mg of the product LL2 (0.066 mmol, 50%yield). ¹H NMR (300 MHz, CDCl₃): 7.48 (d, J=1 Hz, 2H), 7.32–7.40 (m,6H), 6.98–7.20 (m, 8H), 6.76 (d, J=8 Hz, 2H), 5.70 (s, 2H), 4.06 (t, J=6Hz, 4H), 2.33 (s, 6H), 2.05 (tt, J=6 Hz, 2H), 1.31 (s, 36H).

Example 12 Ligand LL3

According to Scheme B1 and General Procedure B1 Step 2, a mixture of thephenol building block BB27 (100 mg, 0.209 mmol), 1,4-dibromobutane (23mg, 0.105 mmol), and Cs₂CO₃ (130 mgs, 0.4 mmol) in acetone (2 mL) wasstirred at 60° C. for 4 hours. After stirring the benzyl ether1 under anatmosphere of H₂ (500 psi) in the presence of Pd/C (50 mg, 5%, Aldrich)in ethyl acetate (1 mL), EtOH (1 mL) and AcOH (1 drop) at 50° C. for 2h, the product was purified by flash chromatography to give 36 mg of theproduct LL3 (0.043 mmol, 41% yield). ¹H NMR (300 MHz, CDCl₃): 7.25–7.48(m, 1014, 7.02–7.15 (m, 6H), 6.85 (d, J=7 Hz, 2H), 5.92 (s, 2H), 3.91 (sbr, 4H), 2.31 (s, 6H), 1.79 (s br, 4H), 1.31 (s, 36H).

Example 13 Building Block BB28

According to Scheme B1 and General Procedure B1 Step 1, the in situgenerated O-THP protected boronic acid BB20 (4.5 mmol), the protected2-bromophenol building block BB2 (3.7 mmol, 1.64 g), Na₂CO₃ (3 mL of a 2M solution in water, 6 mmol) and dimethoxy ethane (15 mL) were reactedin the presence of Pd(PPh₃)₃ (231 mg, 0.2 mmol) at 85° C. for 16 h.After cleavage of the THP ether and purification, 1.21 g of the productBB28 was obtained (2.66 mmol, 72% yield). ¹H NMR (300 MHz, CDCl₃): 8.15(d br, J=7.5 Hz, 2H), 7.25–7.42 (m, 10H), 6.92–7.08 (m, 3H), 8.62 (t br,J=8 Hz, 2H), 6.23 (d br, J=7 Hz, 2H), 4.05 (s, 2H), 2.45 (s, 3H).

Example 14 Ligand LL4

According to Scheme B1 and General Procedure B1 Step 2, a mixture of thephenol building block BB28 (490 mg, 1.077 mmol), 1,4-dibromobutane (116mg, 0.54 mmol), and Cs₂CO₃ (489 mgs, 1.5 mmol) in acetone (5 mL) wasstirred at 60° C. for 4 hours. After stirring the benzyl ethers under anatmosphere of H₂ (500 psi) in the presence of Pd/C (50 mg, 5%, Aldrich)in ethyl acetate (1 mL), EtOH (1 mL) and AcOH (1 drop) at 50° C. for 2h, the product was purified by flash chromatography to give 320 mg ofthe product LL4 (0.41 mmol, 38% yield). ¹H NMR (300 MHz, CDCl₃): 8.10(d, J=8 Hz, 4H), 7.43 (dd, J=7.5 Hz, 2 Hz, 2H), 7.05–7.33 (m, 20H), 6.81(dd, J=8 Hz, 0.5 Hz, 2H), 6.02 (d, 2H), 3.8 (s br, 4H), 2.33 (s, 6H),1.68 (s br, 4H).

Example 15 Ligand LL5

According to Scheme B1 and General Procedure B1 Step 2, a mixture of thephenol building block BB28 (1.202 g, 2.64 mmol),propane-1,3-diol-di-p-tosylate (506 mg, 1.32 mmol), Cs₂CO₃ (1.63 g, 5mmol) in acetone (5 mL) was stirred at 60° C. for 16 hours. Afterstirring the benzyl ethers under an atmosphere of H₂ (500 psi) in thepresence of Pd/C (20 mg, 5%, Aldrich) in ethyl acetate (2 mL) and EtOH(2 mL) at 50° C. for 2 h, the product was purified by flashchromatography to give 630 mg of the product LL5 (0.82 mmol, 62%). ¹HNMR (300 MHz, CDCl₃): 8.18 (d, J=8 Hz, 4H), 7.09–7.39 (m, 18H),6.88–9.95 (m, 4H), 6.30 (d, 2H), 5.55 (s, 2H), 3.95 (t, 4H), 2.35 (s,6H), 2.14 (tt, 2H). ¹H NMR (300 MHz, CDCl₃): 8.18 (d, J=8 Hz, 4H),7.09–7.39 (m, 18H), 6.88–9.95 (m, 4H), 6.30 (d, 2H), 5.55 (s, 2H), 3.95(t, 4H), 2.35 (s, 6H), 2.14 (tt, 2H).

Example 16 Building Block BB29

According to Scheme B1 and General Procedure B1 Step 1, the in situgenerated O-THP protected aryl boronic acid BB20 (0.7 mmol), theprotected 2-bromophenol building block BB9 (0.5 mmol, 226 mg), Na₂CO₃(0.5 mL of a 2 M solution in water, 1 mmol) and dimethoxy ethane (7 mL)were reacted in the presence of Pd(PPh₃)₃ (80 mg, 0.07 mmol) at 85° C.for 16 h. After cleavage of the THP ether and purification, 135 mg ofthe product BB29 was obtained (0.29 mmol, 58% yield). ¹H NMR (300 MHz,CDCl₃): 8.45 (s, 1H), 8.05 (d, J=8.5 Hz, 2H), 7.75 (d, J=8.5 Hz, 2H),7.22–7.45 (m, 10H), 7.02–7.10 (m, 2H), 6.95 (t, J=7.5 Hz, 1H), 6.80 (t,J=7 Hz, 2H), 6.05 (d, J=8 Hz, 2H), 4.05 (s, 2H), 2.48 (s, 3H).

Example 17 Ligand LL6

According to Scheme B1 and General Procedure B1 Step 2, a mixture of thephenol building block BB29 (135 mg, 0.29 mmol),propane-1,3-diol-di-p-tosylate (56 mg, 0.146 mmol), and Cs₂CO₃ (196 mgs,0.6 mmol) in acetone (2 mL) was stirred at 60° C. for 16 hours. Afterstirring the benzyl ether protected intermediate under an atmosphere ofH₂ (500 psi) in the presence of Pd/C (50 mg, 5%, 57% H₂O, JohnsonMathey) in THF (1 mL) and EtOH (1 mL) at 50° C. for 2 h, the product waspurified by flash chromatography (Ethylacetate/hexane=1/10) to give 50mg of the product LL6 (0.062 mmol, 43%). ¹H NMR (300 MHz, CDCl₃): 7.35(dd, J=7.5 Hz, 1.5 Hz, 2H), 7.18 (t, J=7.5 Hz, 2H), 7.05 (t, J=7.5 Hz,2H), 6.99 (d, J=1.5 Hz, 2H), 6.85 (s, 2H), 6.81 (d, J=1.5 Hz, 2H), 6.72(d, J=8 Hz, 2H), 4.0 (t, J=5.5 Hz, 4H), 2.70–2.80 (m, 8H), 2.35 (s, 6H),2.18–2.46 (m, 4H), 2.02 (tt, J 5.5 Hz, 2H), 1.50–1.78 (m, 20H).

In another experiment, the benzyl ether protected intermediate wasisolated in 80% yield. ¹H NMR (300 MHz, CDCl₃): 8.51 (s, 2H), 8.05 (d,J=7.5 Hz, 4H), 7.85 (d, J=7.5 Hz, 4H), 7.12–7.48 (m, 18H), 6.98 (t,J=7.5 Hz, 2H), 6.82 (t, J=7.5 Hz, 2H), 6.70 (t, J=7.5 Hz, 4H), 6.51 (d,J=8 Hz, 2H), 5.90 (d, J=7.5 Hz, 4H), 3.94 (s, 4H), 3.88 (t, 4H), 2.45(s, 3H), 2.01–2.05 (m, 2H).

Additional ligands synthesized in a manner similar to that describedaccording to Scheme B1 include:

Example 18 Ligand LL25

A mixture of the 2-bromophenol benzyl ether BB 17 (319 mg, 0.84 mmol),the diboronic ester BB24 (604 mg, 1.26 mmol), K₃PO₄ (318 mg, 1.5 mmol)and DMF (5 mL) was degassed with argon. Pd(PPh₃)₃ (230 mg, 0.2 mmol, 10mol %) was added and the resulting mixture was stirred at 85° C. for 16h under argon. After removal of the solvent in vacuo, the crude mixturewas purified by flash chromatography to give 80 mg of the bridgedintermediate. After stirring the benzyl ether intermediate under anatmosphere of H₂ (500 psi) in the presence of Pd/C (20 mg, 5%, Aldrich)in THF (1 mL) and EtOH (1 mL) at 50° C. for 2 h, the product waspurified by flash chromatography (Ethylacetate/hexane=1/10) to give 34mg of the product LL25. ¹H NMR (300 MHz, CDCl₃): 7.32 (dd, J=7 Hz, 1 Hz,2H), 7.21 (td, J=7.5 Hz, 1 Hz, 2H), 6.9–7.13 (m, 12H), 6.76 (d, J=7.5Hz, 2H), 5.54 (s, 2H), 4.01 (t, J=6 Hz, 4H), 2.37 (s, 6H), 2.31 (s, 6H),2.13 (s, 6H), 2.03–2.5 (m, 2H).

Example 19 Detailed Example of 2-Br Substituted, Upper-ring Protected,Lower Ring Deprotected Building Block Synthesized According to SchemeB3, Step 1

To a solution of 690 mg (5.0 mmol) of 2-bromophenol-6-boronic acid and1.70 g (4.95 mmol) of 2,6-dibromo-4-methylphenol benzyl ether in 15 mLof degassed dme was added 289 mg (0.25 mmol, 5 mol %) Pd(PPh₃)₄ and 3.2mL of degassed 2.0 M aq. Na₂CO₃. After heating to 80° C. for 4 h, thereaction mixture was cooled to RT and poured into ether. Isolation andconcentration of the organic layer, followed by column chromatography(silica gel, 10% ethyl acetate/hexanes eluent), provided 604 mg (33%) ofpure product as a white solid. ¹H NMR (300 MHz, CDCl₃): 2.41 (s, 3H);4.72 (s, 2H), 6.73 (s, 1H); 7.0–7.6 (overlapping multiplets, 11H).

Example 20 Detailed Example of Bridged, Upper-ring 2-Br SubstitutedBuilding Block Synthesized According to Scheme B3, Step 2

To a solution of 604 mg (1.64 mmol) of2-bromo-4-methyl-6-(2-hydroxyphenyl)phenol benzyl ether and 315 mg (0.82mmol) of 1,3-propanediol di-p-tosylate in 10 mL of acetone was added1.11 g (3.3 mmol) of Cs₂CO₃. After stirring at RT for 16 h, the soln.was filtered and the volitiles were removed. Column chromatography(silica gel, 10% ethyl acetate/hexanes eluent) provided 221 mg (35%) ofthe product as a white solid. ¹H NMR (300 MHz, CDCl₃): 1.96 (m, 2H);2.35 (s, 6H); 3.91 (t, 4H); 4.52 (s, 4H), 6.8–7.6 (overlappingmultiplets, 22H).

Example 21 Detailed Example of a Ligand Synthesized According to SchemeB3, Step 3

To a solution of 100 mg (0.13 mmol) of the dibromo building blockdescribed in Example 20 above dissolved in 5 mL of degassed dme wasadded 84 mg (0.51 mmol) of 2,4,6-trimethylphenylboronic acid, 15 mg(0.013 mmol, 10 mol %) of Pd(PPh₃)₄ and 150 μL of degassed 2.0 M aq.Na₂CO₃. After heating to 85° C. for 16 h, the reaction mixture wascooled to RT and poured into ether. Isolation and concentration of theorganic layer, followed by column chromatography (silica gel, 5% ethylacetate/hexanes eluent), provided 48 mg (42%) of the dibenzyl protectedproduct as a white solid. ¹H NMR (CDCl₃): 1.88 (m, 2H); 2.10 (s, 12H);2.34 (s, 6H); 2.35 (s, 6H); 3.81 (t, 4H); 4.21 (s, 4H), 6.3–7.6(overlapping multiplets, 26H).

After hydrogenation (200 psi H₂, 50° C.) of the dibenzyl product in 5 mLof 1:1 EtOAc/EtOH with 50 mg 5% Pd/C catalyst for 3 h, purification bycolumn chromatography (silica gel, 10% ethyl acetate/hexanes eluent)gave 27 mg (71%) of the ligand. ¹H NMR (300 MHz, CDCl₃): 2.0–2.1(overlapped peaks, 14H); 2.30 (s, 6H); 2.34 (s, 6H); 4.02 (t, 4H); 5.40(s, 2H); 6.7–7.6 (overlapping multiplets, 16H).

Example 22 Additional Example of a Ligand Synthesized According toScheme B3, Step 3

Solutions of 141 μL of 2 M o-tolMgBr in THF and 141 μL of 0.5 M ZnCl₂ inTHF were combined in 1 mL of anhydrous THF and allowed to react at RTfor 1 h. To this solution was added 55 mg (0.13 mmol) of the dibromobuilding block described in Example 20 above, and 1.0 mg (0.003 mmol, 2mol %) of Pd(P^(t)Bu₃)₂. The mixture was diluted with 2 mL of THF and 1mL of NMP, sealed, and heated to 80° C. for 2 h. After cooling to RT,the THF was removed in vacuo and the product was diluted with ether andwashed with saturated brine. Isolation and concentration of the organiclayer, followed by column chromatography (silica gel, 5% ethylacetate/hexanes eluent), provided 39 mg (69%) of the dibenzyl protectedproduct as a white solid. ¹H NMR (CD₂Cl₂): 1.97 (m, 2H); 2.18 (s, 6H);2.35 (s, 6H); 3.91 (m, 4H); 4.19 (s, 4H), 6.45 (d, 4H); 6.7–7.5(overlapping multiplets, 26H).

After hydrogenation (100 psi H₂, 40° C.) of the dibenzyl product in 5 mLof 1:1 EtOAc/EtOH with 50 mg 5% Pd/C catalyst for 3 h, purification bycolumn chromatography (silica gel, 10% ethyl acetate/hexanes eluent)gave 23 mg (77%) of the ligand. ¹H NMR (300 MHz, CD₂Cl₂): 1.85 (m, 2H);2.20 (s, 6H); 2.31 (s, 6H); 4.10 (t, 4H); 5.32 (s, 2H); 6.7–7.6(overlapping multiplets, 20H).

Part C: Synthesis of (S,S)-Bridged Bis(Biphenylphenol) Ligands:

Example 23 A Biaryl Thiophenol Building Block Synthesized According toScheme C1 Step 1

A mixture of the S-THP protected boronic acid building block BB21 (7mmol), the protected 2-bromophenol BB14 (5 mmol, 1.6 g), Na₂CO₃ (4 mL ofa 2 M solution in water, 8 mmol) and dimethoxy ethane (15 mL) wasdegassed with argon (10 min). Pd(PPh₃)₃ (280 mg, 0.25 mmol, 5%) wasadded and the resulting mixture was stirred at 85° C. for 16 h underargon. Ethyl acetate (EA, 15 mL) was added and the mixture was driedover Na₂SO₄. After filtration, the solvent was removed and the residuewas dissolved in CH₂Cl₂ (10 mL). HCl (1 mL, 37%) was added and theresulting mixture was stirred at 40° C. for 2 h. Brine was added and themixture was extracted with ethyl acetate, dried over Na₂SO₄, andpurified by flash chromatography (Ethylacetate/hexane=1/10) to give 1.4g of the product BB30 (4 mmol, 80% yield). ¹H NMR (300 MHz, CDCl₃):7.58–7.63 (d br, J=7 Hz, 2H), 7.30–7.42 (m, 6H), 7.19–7.25 (m, 3H), 3.49(s, 1H), 3.14 (s, 3H), 1.33 (s, 9H).

Example 24 A bis aryl Building Block Synthesized According to Scheme C1Step 1

According to Scheme C1 Step1, the compound BB31 was synthesized in about50% yield. ¹H NMR (300 MHz, CDCl₃): 7.56–7.63 (d br, J=7 Hz, 2H),7.38–7.45 (m, 4H), 7.25–7.35 (m, 2H), 7.18–7.25 (m, 4H), 3.47 (s, 1H),3.17 (s, 3H).

Example 25 A Ligand Synthesized According to Scheme C1 Step 2

A mixture of the biaryl thiophenol building block BB31(55 mg, 0.188mmol), the corresponding dibromide (α,α′-dibromo-o-xylene, 25 mg, 0.094mmol), and K₂CO₃ (55 mgs, 0.4 mmol) in acetone (2 mL) was stirred at 60°C. for 4 hours. After filtration, the solvent was removed and theresidue was dissolved in CH₂Cl₂ (3 mL). BBr₃ (1.5 mL of a 1 M solutionin CH₂CL₂, 1.5 mmol) was added and the resulting mixture was stirred atroom temperature for 2 h. Brine was added and the mixture was extractedwith ethyl acetate, dried over Na₂SO₄, and purified by flashchromatography (Ethylacetate/hexane=1/10) to give 46 mg of the productLL26 (0.07 mmol, 75% yield). ¹H NMR (300 MHz, CDCl₃): 7.50–7.55 (d br,J=7 Hz, 4H), 7.41–7.48 (t br, J=7 Hz, 4H), 7.30–7.38 (m, 4H), 7.23–7.29(m, 8H), 6.98–7.08 (m, 8H), 3.95 (m, 4H).

Additional ligands that are synthesized in a manner similar to thatdescribed in Scheme C1:

Example 26 A Ligand Synthesized According to Scheme C2 Step 2

A mixture of the protected bis aryl thiophenol (BB31) (104 mg, 0.356mmol), the corresponding dibromide (1,2-dibromobenzene, 42 mg, 0.178mmol), NaOtBu (48 mg, 0.5 mmol) in degassed toluene (2 mL) was added toa solution of Pd(dba)₂ (20 mg, 0.036 mmol, 10%) and Xantphos (41 mg,0.712 mmol, 20%), and the resulting mixture was stirred at 110° C. for16 h under argon. After filtration, the solvent was removed and theresidue was dissolved in CH₂Cl₂ (5 mL). BBr₃ (2 mL of a 1 M solution inCH₂CL₂, 2 mmol) was added and the resulting mixture was stirred at roomtemperature for 2 h. Brine was added and the mixture was extracted withethylacetate, dried over Na₂SO₄, and purified by flash chromatography(ethylacetate/hexane=1/10) to give 57 mg of the product LL42 (0.091mmol, 51% yield). ¹H NMR (300 MHz, CDCl₃): 7.15–7.45 (m, 14H), 7.05–7.15(m, 8H), 6.90 (t, J=7.5 Hz, 2H), 4.04 (s, 2H).

Additional ligands that are synthesized in a manner similar to thatdescribed in Scheme C2:

Example 27 A Ligand Synthesized by Combining Schemes C1 and C2

According to Scheme C1 Step 2, the thiophenol building block BB31 (38mg, 0.13 mmol), the corresponding dibromide (2-bromobenzylbromide, 33mg, 0.13 mmol), and K₂CO₃ (110 mgs, 0.8 mmol) in acetone (2 mL) wasstirred at 60° C. for 2 hours. After workup and cleavage of the methylethers, and purification 54 mg of the intermediate were isolated (0.117mmol, 90%). According to Scheme C2 Step 2, a mixture of the thiophenolbuilding block BB31 (34 mg, 0.117 mmol), the intermediate (54 mg, 0.117mmol), NaOtBu (20 mg, 0.2 mmol), Pd(dba)₂ (3 mgs, 0.006 mmol), andXantphos (6 mg, 0.012 mmol) in toluene (2 mL) was stirred at 110° C. for16 hours. After workup and cleavage of the methyl ethers, andpurification 88 mg of the ligand LL45 was isolated (0.101 mmol, 54%). ¹HNMR (300 MHz, CDCl₃) (dimethyl ether!): 7.55–7.62 (m, 4H), 7.30–7.42 (m,12H), 7.22–7.28 (m, 2H), 7.12–7.25 (m, 8H), 7.01–7.11 (m, 4H), 4.12 (m,2H), 3.10 (s, 3H), 3.05 (s, 3H).

Example 28 A Ligand Synthesized According to Scheme C3

A mixture of the boronic acid (0.8 mmol), the (S,S)-bridged bis(arylbromide) (0.4 mmol, 161 mg, prepared as shown above), Na₂CO₃ (0.5 mL ofa 2 M solution in water, 1.5 mmol) and dimethoxy ethane (5 mL) wasdegassed with argon (10 min). Pd(PPh₃)₄ (92 mg, 0.08 mmol, 20%) wasadded and the resulting mixture was stirred at 85° C. for 16 h underargon. Ethyl acetate (15 mL) was added and the mixture was dried overNa₂SO₄. After filtration, the solvent was removed and the residue wasdissolved in CH₂Cl₂ (10 mL). BBr₃ (2 mL of a 1 M solution in CH₂CL₂, 2mmol) was added and the resulting mixture was stirred at roomtemperature for 2 h. Brine was added and the mixture was extracted withEA, dried over Na₂SO₄, and purified by flash chromatography(Ethylacetate/hexane=1/10) to give 37 mg of the product LL46 (0.06 mmol,15% yield). ¹H NMR (300 MHz, CDCl₃): 7.52–7.58 (d br, J=7 Hz, 4H),7.41–7.48 (t br, J=7 Hz, 4H), 7.23–7.39 (m, 12H), 6.98–7.12 (m, 4H),5.10 (s, 2H), 2.85 (s, 4H).

Additional ligands that are synthesized in a manner similar to thatdescribed in Scheme C3:

Part D:

Example 29 Synthesis of (O,S)-Bridged Bis(Biphenylphenol) Ligands

A mixture of the MOM ether protected 2-bromophenol (176 mg, 0.43 mmol),the diboronic ester BB25 (110 mg, 0.216 mmol), K₃PO₄ (150 mg, 0.7 mmol)and DMF (2 mL) was degassed with argon. Pd(PPh₃)₄ (46 mg, 0.04 mmol) wasadded and the resulting mixture was stirred at 85° C. for 16 h underargon. After removal of the solvent in vacuo, the crude mixture waspurified by flash chromatography to give 81 mg of the intermediate.After cleavage of the MOM ether (HCl, THF, MeOH) and purification, 40 mgof the product LL49 was obtained (0.05 mmol, 23% yield). ¹H NMR (300MHz, CDCl₃): 8.10 (d, J=7.5 Hz, 4H), 7.15–7.45 (m, 21H), 7.05–7.12 (m,2H), 6.88 (d, J=8.5 Hz, 1H), 6.01 (s, 1H), 4.89 (s, 1H), 3.95 (t, J=6Hz, 2H), 2.75 (t, J=7 Hz, 2H), 2.37 (s, 3H), 2.32 (s, 3H), 1.75–1.85 (m,2H), 1.60–1.70 (m, 2H).

Part E: Synthesis of (N,N)-Bridged Bis(Biphenylphenol) Ligands:

Example 30 Synthesis of bis aryl building blocks BB32 and BB33

n-BuLi (2.6 mmol, from a 1.6 M solution in hexanes) was added slowly toa solution of the benzyl ether protected 2-bromophenol (2.47 mmol) inTHF (5 mL, anhydrous) at −78° C. under an atmosphere of argon. Afterstirring for 10 min at that temperature, triisopropyl borate (645 μL,2.8 mmol) was added slowly and the temperature was allowed to come toroom temperature (30 min). After stirring for another 30 min, thesolvent was removed and the crude boronic acid was used without furtherpurification. A mixture of the boronic acid (750 mg, 2.5 mmol), 1,2dibromobenzene (2.36 g, 10 mmol), Na₂CO₃ (2 mL of a 2 M solution inwater, 4 mmol) and dimethoxy ethane (15 mL) was degassed with argon.Pd(PPh₃)₃ (144 mg, 0.125 mmol, 10%) was added and the resulting mixturewas stirred at 85° C. for 16 h under argon. Ethyl acetate (30 mL) wasadded and the mixture was dried over Na₂SO₄. After filtration, the crudeproduct was purified by flash chromatography (ethylacetate/hexane=1/10)to give 762 mg of the benzyl ether product BB32 (1.6 mmol, 65% yield).The methyl ether product BB33 was prepared similarly.

Example 31 Synthesis of (NH,NH)-Bridged Biaryl Phenyl Methyl EtherLigand

A mixture of the methyl ether building block BB33 (140 mg, 0.348 mmol),1,4-diaminobutane (15 mg, 0.174 mmol), NaOtBu (48 mg, 0.5 mmol) andtoluene (2 mL) was degassed with argon. Pd(dba)₂ (9 mg, 0.015 mmol) anddppf (1,1′-bis(diphenylphosphino)ferrocene, 17 mg, 0.03 mmol) were addedand the resulting mixture was stirred at 100° C. for 16 h under argon.After removal of the solvent in vacuo, the crude mixture was purified byflash chromatography to give 51 mg of the product LL50 (0.068 mmol, 39%yield). ¹H NMR (300 MHz, CDCl₃): 7.82–7.90 (m, 4H), 7.61–7.79 (m, 2H),7.32–7.55 (m, 8H), 7.21–7.29 (m, 4H), 7.09–7.19 (m, 4H), 6.65–6.89 (m,4H), 3.90–4.05 (m, 2H), 3.05–3.15 (m, 4H), 2.95 (t, 6H), 2.33 (s, 6H),1.62–1.80 (m, 4H).

Example 32 Synthesis of (NMe,NMe)-bridged Biaryl Phenol Ligand LL51

A mixture of the substituted phenylbromide (benzyl ether, BB32, 133 mg,0.278 mmol), 1,4-diaminobutane (12 mg, 0.139 mmol), NaOtBu (48 mg, 0.5mmol) and toluene (2 mL) was degassed with argon. Pd(dba)₂ (9 mg, 0.015mmol) and dppf (17 mg, 0.03 mmol) were added and the resulting mixturewas stirred at 100° C. for 16 h under argon. After removal of thesolvent in vacuo, the crude mixture was purified by flash chromatographyto give 31 mg of the intermediate. A mixture of this intermediate withformic acid (0.5 mL) and paraformaldehyde (0.5 mL of a 37% solution inH₂O) was stirred for 30 min at 80° C. Na₂CO₃ (5 mL of a 2M aq. Solution)was added and the mixture was extracted with ethyl acetate. Afterstirring the benzyl ether intermediate under an atmosphere of H₂ (500psi) in the presence of Pd/C (50 mg, 5%, Aldrich) in EA (1 mL), EtOH (1mL) at 50° C. for 2 h, the crude product was purified by flashchromatography to give 15 mg of the product LL51. ¹H NMR (300 MHz,CDCl₃): 10.23 (s, 2H), 7.82 (t, 4H), 7.62 (d, 2H), 6.42–7.52 (m, 4H),7.15–7.41 (m, 14H), 7.08 (t, 2H), 7.02 (d, 2H), 2.42–2.60 (m, 10H), 2.30(s, 3H), 2.25 (s, 3H), 1.42–1.12 (m, 4H).

Complexes used in some of the examples:

Example 33 Synthesis of Complex C1

46.3 mg (67 mmol) LL1 in 6 mL toluene were combined with 36.3 mg (67mmol) of HfBz₄ in 6 mL toluene. The mixture was stirred for 10 min andslowly concentrated by removing the solvent with a stream of inert gas.A white solid material was isolated. The 1H-NMR is consistent with onesymmetrical compound. The ¹H-NMR spectrum indicates the presence oftoluene in the isolated product. 1H-NMR in C₆D₆ (δ in ppm): aromaticprotons: 7.83 (d), 7.6–6.5 (m), 6.05 (d) bridge CH₂—O— protons 4.1 (m),3.6 (m) Hf-CH₂Ph protons: 2.21 (d), 1.1 (d) ^(t)Bu protons: 1.24 (s),bridge CH₂—CH₂—O— protons 0.83 (m), 0.45 (m).

Example 34 Synthesis of Complex C2

50 mg (64.85 mmol) LL5 and 23 mg Hf(NMe₂)₄ were combined in 8 mLtoluene. The reaction mixture was placed in sand bath at 60–70° C. After1 hour, a stream of Ar was used to remove the solvent. A dry whiteproduct was obtained. The 1H-NMR is consistent with a C2 symmetricbisamide complex and indicates the presence of toluene in the isolatedproduct. 1H-NMR in C₆D₆ (δ in ppm): 8.39 (d), 8.09 (d), 7.5–6.6 (m),5.02 (d), 3.8 (m), 3.25 (m), 2.15 (s), 1.82 (s), 1.05 (m).

Example 35 Synthesis of Complex C3

64 mmol of complex C2 is dissolved in 5 mL toluene and 100 mg ofMe₃Si—Cl was added. After reaction overnight, volatile products and thesolvent were removed. The reaction mixture was taken up in 2 ml tolueneand 400 ul Cl₂SiMe₂ were added. A white precipitate formed within 30min. 31 mg (45%) of the bischloride complex 3 was isolated. The 1H-NMRis consistent with one C2 symmetric bischloride complex (on NMRtimescale) and indicates the presence of toluene in the isolatedproduct. 1H-NMR in CD₂Cl₂ (δ in ppm): 8.38 (d), 8.12 (d), 7.6–7.05 (m),6.75 (m), 4.61 (d), 4.21 (m), 3.7 (m), 2.4 (s), 0.1.72 (m).

Example 36 Synthesis of Complex C3

31.4 mmol ligand LL5 is dissolved in 450 ul toluene. 31.6 mmolHfCl₂Bz₂.Et₂O is dissolved in 900 ul toluene and added to the ligandsolution. The reaction mixture was placed in a sand bath at 70° C. for 1hour. The reaction mixture was allowed to cool to room temperatureovernight. The supernatant liquid was removed from the white solidproduct. The solid material was dried. Yield: 25 mmol (80%).

Example 37 Synthesis of Complex C4

37.6 mg (54 mmol) LL1 in 8 mL toluene was combined with 24.8 mg (54mmol) of ZrBz₄ in 6 mL toluene. The mixture was stirred for 1–2 min andslowly concentrated by removing the solvent with a stream of inert gas.A pale yellow solid material was isolated. The ¹H-NMR is consistent withone symmetrical compound. The ¹H-NMR spectrum indicates the presence oftoluene in the isolated product. ¹H-NMR in C₆D₆ (δ in ppm): aromaticprotons: 7.91 (d), 7.7–6.6 (m), 6.07 (d) bridge CH₂—O— protons 4.02 (m),3.54 (m) Hf-CH₂Ph protons: 2.46 (d), 1.24 (d) tBu protons: 1.17 (s),bridge CH₂—CH₂—O— protons 0.86 (m), 0.51 (m).

Example 38 Synthesis of Complex C5

12.1 mg HfCl₂Bz₂.Et₂O (24 mmol) in 900 uL toluene was added to 20.4 mgLL6 (25 mmol) in 450 uL toluene. 150 uL toluene were added and thereaction mixture was placed in a sand bath at 80° C. for 1.5 hours. Thesolution was allowed to cool to room temperature. Colorless crystalsformed which were isolated by decanting the supernatent liquid. Yield14.4 mg (54%). ¹H-NMR in CD₂Cl₂ (δ in ppm): 7.7–6.9 ppm (aromaticprotons), 6.1 ppm (d), 4.25 (m), 4.05 (m), 3.1–2.6 (m), 2.6–2.05 (m),2.05–1.3 (m). Single crystal X-ray analysis was performed.Crystallographic data: for C57H58Cl2HfO4, M=1056.42. Orthorombic crystalsystem, space group Pcca, unitcell dimentions: a=22.851(10) Å,b=14.984(5) Å, c=16.454 (7) Å, Z=4, Dc=1.253 mg/m³, 15684 reflectionscollected. The structure was solved by by direct methods and refined byfull-matrix least squares on F². The final refinement converged atR₁=0.0815 and wR₂=0.2011 for I>2σ (I) and R₁=0.1561 and wR₂=0.2206 forall data. X-ray structure is shown in FIG. 1 a and 1 b.

Example 39 Synthesis of Complex C6

16 mg HfCl₂Bz₂*Et₂O (31.7 mmol) in 800 uL toluene was added to 26 mg(31.7 mmol) LL3 in 400 uL toluene. The reaction mixture was placed in asand bath at 70° C. for 35 min. The reaction mixture was allowed to coolto room temperature over night and was cooled to −30° C. for 1 hour. Thecolorless crystalline material was separated from the solution anddried. Yield: 30 mg (87%). 1H-NMR in CD₂Cl₂ (δ in ppm): 7.64–7.02 ppm(aromatic protons), 4.62 (m), 3.94 (m), 2.36 (s), 1.40 (s), 1.20 (m).

Example 40 Synthesis of Complex C7

11.3 mg HfCl₂Bz₂.Et₂O (22.3 mmol) in 500 uL toluene was added to 18 mg(22.3 mmol) LL52 in 300 uL toluene. The reaction mixture was placed in asand bath at 70° C. for 90 min. The reaction mixture was allowed to coolto room temperature for 100 min and was cooled to −30° C. over night.The powdery crystalline material was separated from the solution anddried. Yield: 14.3 mg (61%). ¹H-NMR in CD₂Cl₂ (δ in ppm): 8.36 (d), 8.12(d), 7.5–7.0 ppm (aromatic protons), 4.44 (m), 4.52 (m), 4.15 (m), 3.67(m), 2.40 (s), 1.7 (m).

Example 41 Propylene Polymerizations Using Metal-ligand Compositions. ATotal of One Hundred and Eight (108) Separate Polymerization Reactionswere Performed as Described Herein

Preparation of the polymerization reactor prior to injection of catalystcomposition: A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor. The reactorwas then closed, 0.10 mL of a 0.02 M solution of group 13 reagents intoluene and 3.9 mL of toluene were injected into each pressure reactionvessel through a valve. The identity of the group 13 reagent solution isgiven in Tables 1–3. The temperature was then set to the appropriatesetting (with specific temperatures for each polymerization being listedin Tables 1–3, below), and the stirring speed was set to 800 rpm, andthe mixture was exposed to propylene at 100 psi pressure. A propylenepressure of 100 psi in the pressure cell and the temperature settingwere maintained, using computer control, until the end of thepolymerization experiment.

In situ preparation of metal-ligand compositions: The following methodswere employed to prepare the metal-ligand compositions as indicated inthe Tables 1–3. Method A: An appropriate amount of ligand solution (10mM in toluene) was dispensed in a 1 mL glass vial at a scale of 0.4–0.75mmol. To the 1 mL glass vial containing the ligand solution was added anequimolar amount of metal precursor solution (10 mM in toluene) to formthe metal-ligand composition solution. The reaction mixture was heatedto 70–80° C. for 1–2 hours. Method B: Similar to Method A except thereaction mixture was heated to 60° C. for 1–2 hours. Method C: Similarto Method A except the reaction mixture was heated to 80° C. for 1–2hours. The residual solvent and volatile byproducts were removed byblowing a stream of Argon over the 1 mL vial. The composition wasredissolved in toluene prior to addition of alkylation and activatorsolution. Method D: Similar to Method A except the concentration ofligand and metal precursor solutions were 5 mM. The reaction mixture wasallowed to sit at room temperature for 35 min and than was heated to70–80° C. for 10 min. Method E: Similar to Method B except theconcentration of ligand and metal precursor solutions were 5 mM. MethodF: Similar to Method A except the concentration of ligand solution was 5mM and metal precursor solution was 10 mM. The reaction mixture washeated for 30 min to 50° C. Method G: Similar to Method A except theconcentration of ligand solution was 15 mM and metal precursor solutionwas 10 mM. The reaction mixture was heated for 1 hour to 70° C. MethodH: Similar to Method A except the concentration of ligand solution was60 mM and metal precursor solution was 5 mM. The reaction mixture washeated for 45 min to 70° C. Method I: Similar to Method G except theconcentration of ligand solution was 25 mM and metal precursor solutionwas 5 mM. Method J: Similar to Method H except the concentration ofligand solution was 12 mM and metal precursor solution was 5 mM.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (“ABF₂₀”). The molarity ofthis solution is indicated in the “activation method” of the individualexample described below. The solution is heated to approximately 85° C.to dissolve the reagent. The “group 13 reagent” solution is either asolution of triisobutyl aluminium (“TIBA”) or a solution oftrimethylaluminium (“TMA”) or a solution of Modified Methylaluminoxane3A (from Azko Chemical Inc., Chicago, Ill.) (“MMAO”) or a solution ofPolymethylaluminoxane-Improved Process (from Azko Chemical Inc.,Chicago, II) (“PMAO”), all “group 13 reagent” solutions were solutionsin toluene. The molarity of the solutions used is indicated in the“activation method” of the individual example described below.

Activation methods and Injection of solutions into the pressure reactorvessel, The following methods were employed to activate and inject themetal-ligand compositions for the examples in the Tables 1–3. Method AA:To the metal-ligand composition, 20 mole equivalents (per metalprecursor) of a 500 mM solution of 1-octene in toluene were added to themetal ligand composition in the 1 mL vial. Then, the appropriate amountof the group 13 reagent solution as a 50 mM solution, containing theindicated equivalents group 13 reagent (per metal precursor) in thespecific example, was added to the 1 mL vial. After 45 sec, 1.1 molequivalents (per metal precursor) of the “activator solution” (2.5 mM)was added to the 1 mL vial. About another 30 seconds later, a fractionof the 1 mL vial contents corresponding to the indicated “catalystamount injected” was injected into the prepressurized reaction vesseland was followed immediately by injection of toluene to bring the totalvolume injected to 0.400–0.500 mL. Method BB: similar to Method AAexcept the concentration of the activator solution was 5 mM. Method CC:To the metal-ligand composition, the appropriate amount of the group 13reagent solution as a 50 mM solution, containing the indicatedequivalents group 13 reagent (per metal precursor) in the specificexample, was added to the 1 mL vial. After 40 sec, the indicated amountof the “activator solution” (2.5 mM) was added to the 1 mL vial. Aboutanother 40 seconds later, a fraction of the 1 mL vial contentscorresponding to the indicated “catalyst amount injected” was injectedinto the prepressurized reaction vessel, and was followed immediately byinjection of toluene to bring the total volume injected to 0.400–0.500mL. Method DD: To the metal-ligand composition, the appropriate amountof the group 13 reagent solution (50 mM), containing the indicatedequivalents group 13 reagent (per metal precursor) in the specificexample, was added to the 1 mL vial that was kept at 50–60° C. Afterabout 10 min, the indicated amount of the “activator solution” (2.5 mM)was added to the 1 mL vial. About another 70 seconds later, a fractionof the 1 mL vial contents containing the indicated “catalyst amountinjected” was injected into the prepressurized reaction vessel and wasfollowed immediately by injection of toluene to bring the total volumeinjected to 0.400–0.500 mL.

Polymerization: The polymerization reaction was allowed to continue for60–900 seconds, during which time the temperature and pressure weremaintained at their pre-set levels by computer control. The specificpolymerization times for each polymerization are shown in Tables 1–3.After the reaction time elapsed, the reaction was quenched by additionof an overpressure of carbon dioxide sent to the reactor. Thepolymerization times were the lesser of the maximum desiredpolymerization time or the time taken for a predetermined amount ofmonomer gas to be consumed in the polymerization reaction.

Product work up: Propylene Polymerizations: After the polymerizationreaction, the glass vial insert, containing the polymer product andsolvent, was removed from the pressure cell and removed from the inertatmosphere dry box, and the volatile components were removed using acentrifuge vacuum evaporator. After most of the volatile components hadevaporated, the vial contents were dried thoroughly by evaporation atelevated temperature under reduced pressure. The vial was then weighedto determine the yield of polymer product. The polymer product was thenanalyzed by rapid GPC, as described above to determine the molecularweight of the polymer produced, and by FTIR spectroscopy to determinethe crystallinity index. The melting point of selected samples wasmeasured by DSC, as described above.

TABLE 1 Group 13 catalyst Activity (g complex- reagent Activator acti-amount Polym. polymer/ Mp DSC Mw Metal ation and mole and mol vationinjected temp. Polym. (min * FTIR data (/1000) Ligand precursor methodequiv. equiv. method nmol (Celsius) time (sec) mmol) index (Celsius)(PDI) LL5 HfBz₄ A 6 MMAO 1.1 ABF₂₀ BB 50 110 76 4683 0.8 128 333 (2.0)LL5 HfBz₄ A 6 MMAO 1.1 ABF₂₀ BB 100 130 89 2379 0.82 151 (1.9) LL5 ZrBz₄A 6 MMAO 1.1 ABF₂₀ BB 50 110 182 1079 0.76 108 106 (1.6) LL5 ZrBz₄ A 6MMAO 1.1 ABF₂₀ BB 100 130 298 499 0.68  82 (1.5) LL5 TiBz₄ F 5 PMAO 1.1ABF₂₀ BB 200 90 600 13 0.5 979 (1.9) LL4 HfBz₄ A 6 MMAO 1.1 ABF₂₀ BB 50110 179 1470 0.86 137 1116 (1.7)  LL4 HfBz₄ A 6 MMAO 1.1 ABF₂₀ BB 100130 210 720 0.88 407 (1.7) LL4 ZrBz₄ A 6 MMAO 1.1 ABF₂₀ BB 50 110 375449 0.82 271 (1.6) LL4 ZrBz₄ A 6 MMAO 1.1 ABF₂₀ BB 100 130 601 128 0.82135 (1.7) LL14 HfBz₄ F 5 PMAO 1.1 ABF₂₀ BB 150 90 600 18 0.82 404 (1.7)LL14 ZrBz₄ F 5 MMAO 1.1 ABF₂₀ BB 150 90 600 17 0.63 nd LL18 HfBz₄ A 6MMAO 1.1 ABF₂₀ CC 60 110 94 2866 0.84 407 (2.0) LL18 HfBz₄ A 6 MMAO 1.1ABF₂₀ CC 60 130 114 2136 0.84 266 (2.1) LL18 ZrBz₄ A 6 MMAO 1.1 ABF₂₀ CC60 110 201 767 0.74 122 (1.8) LL18 Zr(NMe₂)₄ C 10 TMA 1.1 ABF₂₀ DD 100110 111 992 0.74 123 (1.7) LL21 HfBz₄ A 6 MMAO 1.1 ABF₂₀ CC 40 110 915048 0.86 134 526 (2.5) LL21 HfBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 130 92 29080.86 133 181 (2.2) LL21 ZrBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 110 128 1366 0.77232 (1.8) LL21 ZrBz₄ A 6 MMAO 1.1 ABF₂₀ CC 100 130 257 814 0.77 117(1.8) LL23 HfBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 110 108 2664 0.84 368 (2.0)LL23 ZrBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 110 250 660 0.73 118 (1.8) LL20HfBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 110 600 145 0.91 2764 (1.5)  LL20 ZrBz₄ A6 MMAO 1.1 ABF₂₀ CC 60 110 488 376 0.76 627 (1.6) LL49 HfBz₄ A 6 MMAO1.1 ABF₂₀ CC 75 75 900 46 0.87 1678 (2.5)  LL49 ZrBz₄ A 6 MMAO 1.1 ABF₂₀CC 75 75 626 103 0.89  24 (1.5)

TABLE 2 Group 13 catalyst Activity (g complex- reagent Activator acti-amount Polym. polymer/ Mp DSC Mw Metal ation and mole and mol vationinjected temp. Polym. (min * FTIR data (/1000) Ligand precursor methodequiv. equiv. method nmol (Celsius) time (sec) mmol) index (Celsius)(PDI) LL1 HfBz₄ A 5 MMAO 1.1 ABF₂₀ AA 50 90 133 1973 0.32 416 (1.6) LL1ZrBz₄ A 5 MMAO 1.1 ABF₂₀ AA 50 90 260 681 0.60 577 1.6) LL1 HfBz₄ A 5MMAO 1.1 ABF₂₀ BB 100 110 293 295 0.57 184 (1.8) LL1 ZrBz₄ A 5 MMAO 1.1ABF₂₀ BB 100 110 126 930 0.30 162 (1.9) LL7 HfBz₄ A 5 MMAO 1.1 ABF₂₀ BB100 110 141 758 0.78 378 (1.8) LL7 ZrBz₄ A 5 MMAO 1.1 ABF₂₀ BB 100 110165 536 0.65 203 (1.9) LL2 HfBz₄ A 6 MMAO 1.1 ABF₂₀ CC 75 110 900 830.92 146 123 (1.6) LL2 HfBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 75 489 265 0.89151 781 (1.8) LL2 ZrBz₄ A 6 MMAO 1.1 ABF₂₀ CC 75 110 163 785 0.89 137113 (1.5) LL2 ZrBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 75 149 1643 0.87 142 393(1.6) LL3 HfBz₄ A 6 MMAO 1.1 ABF₂₀ CC 150 110 494 123 0.95 149 197 (2.1)LL3 HfBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 75 602 153 0.93 153 977 (1.8) LL3ZrBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 110 900 91 0.90 142 298 (1.8) LL10 HfBz₄A 6 MMAO 1.1 ABF₂₀ CC 150 110 900 30 0.93 149 202 (2.4) LL10 ZrBz₄ A 6MMAO 1.1 ABF₂₀ CC 60 110 900 38 0.89 139 322 (2.2) LL53 HfBz₄ B 6 MMAO1.1 ABF₂₀ CC 150 110 485 111 0.93 122 (1.5) LL53 ZrBz₄ B 6 MMAO 1.1ABF₂₀ CC 150 110 124 629 0.92  85 (1.6) LL54 HfBz₄ B 6 MMAO 1.1 ABF₂₀ CC150 110 153 449 0.94  99 (1.5) LL54 ZrBz₄ B 6 MMAO 1.1 ABF₂₀ CC 150 110104 744 0.91 106 (1.6) LL6 HfBz₄ A 6 MMAO 1.1 ABF₂₀ CC 75 110 900 1050.89 146 526 (1.9) LL6 HfBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 75 900 107 0.90150 1969 (1.7)  LL6 ZrBz₄ A 6 MMAO 1.1 ABF₂₀ CC 75 110 709 152 0.86 135164 (1.5) LL6 ZrBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 75 209 598 0.90 139 317(1.5) LL6 Hf(NMe₂)₄ C 10 TMA 1.1 ABF₂₀ DD 150 110 126 687 0.91 197 (1.8)LL6 Hf(NMe₂)₄ C 10 TMA 1.1 ABF₂₀ DD 150 110 96 966 0.87 109 (1.5) LL12HfBz₄ B 6 MMAO 1.1 ABF₂₀ CC 150 110 675 102 0.76  87 (1.5) LL12 ZrBz₄ B6 MMAO 1.1 ABF₂₀ CC 150 110 112 635 0.56  98 (1.6) LL13 HfBz₄ B 6 MMAO1.1 ABF₂₀ CC 150 110 901 29 0.78  83 (1.6) LL13 ZrBz₄ B 6 MMAO 1.1 ABF₂₀CC 150 110 117 649 0.60 109 (1.5) LL9 HfBz₄ D 5 PMAO 1.1 ABF₂₀ BB 100110 600 81 0.65  56 (1.8) LL9 ZrBz₄ E 5 PMAO 1.1 ABF₂₀ BB 100 110 129803 0.47  91 (1.5) LL8 HfBz₄ D 5 PMAO 1.1 ABF₂₀ BB 100 110 600 74 0.66156 (1.6) LL8 ZrBz₄ E 5 PMAO 1.1 ABF₂₀ BB 100 110 194 460 0.48 144 (1.5)LL25 HfBz₄ A 6 MMAO 1.1 ABF₂₀ CC 60 75 617 150 0.77 674 (1.8) LL25 ZrBz₄A 6 MMAO 1.1 ABF₂₀ CC 60 75 159 1172 0.65 144 (2.2)

TABLE 3 Group 13 catalyst Activity (g complex- reagent Activator amountPolym. polymer/ Mp DSC Mw Metal ation and mole and mol activationinjected temp. Polym. (min * FTIR data (/1000) Ligand precursor methodequiv. equiv. method nmol (Celsius) time (sec) mmol) index (Celsius)(PDI) LL46 TiBz4 G 5 MMAO 1.1 ABF₂₀ AA 300 90 900 8 0.51 103 (2.5) LL46ZrBz4 G 5 MMAO 1.1 ABF₂₀ AA 200 110 650 22 0.63 35 (2.7) LL46 HfBz4 H 5MMAO 1.1 ABF₂₀ AA 150 90 314 98 0.75 25 (2.0) LL37 ZrBz4 I 5 MMAO 1.1ABF₂₀ AA 75 90 900 46 0.78 5 (1.4) LL37 ZrBz4 J 5 TIBA 1.1 ABF₂₀ AA 7590 900 36 0.72 4 (3.3) LL48 ZrBz4 H 5 MMAO 1.1 ABF₂₀ AA 150 90 113 4170.57 12 (2.2) LL48 HfBz4 H 5 MMAO 1.1 ABF₂₀ AA 300 90 138 192 0.69 102(2.9) LL48 ZrBz4 G 5 MMAO 1.1 ABF₂₀ AA 200 110 189 170 0.52 41 (2.5)LL48 HfBz4 G 5 MMAO 1.1 ABF₂₀ AA 200 110 312 86 0.50 49 (4.1) LL31 ZrBz4I 5 MMAO 1.1 ABF₂₀ AA 75 90 323 261 0.49 2 (1.2) LL31 HfBz4 I 5 MMAO 1.1ABF₂₀ AA 150 90 304 148 0.69 11 (1.7) LL31 ZrBz4 J 5 TIBA 1.1 ABF₂₀ AA75 90 358 218 0.43 3 (2.6) LL31 HfBz4 J 5 TIBA 1.1 ABF₂₀ AA 75 90 651127 0.57 18 (4.2) LL28 ZrBz4 H 5 MMAO 1.1 ABF₂₀ AA 150 90 80 885 0.52 28(2.0) LL28 HfBz4 H 5 MMAO 1.1 ABF₂₀ AA 300 90 62 779 0.59 93 (1.9) LL28ZrBz4 G 5 MMAO 1.1 ABF₂₀ AA 200 110 105 320 0.46 35 (2.7) LL28 HfBz4 G 5MMAO 1.1 ABF₂₀ AA 200 110 92 455 0.51 80 (2.9) LL29 ZrBz4 A 5 MMAO 1.1ABF₂₀ AA 50 90 160 855 0.51 19 (1.9) LL29 HfBz4 A 5 MMAO 1.1 ABF₂₀ AA 5090 358 437 0.42 115 (1.6) LL30 ZrBz4 I 5 MMAO 1.1 ABF₂₀ AA 75 90 154 6630.38 42 (2.0) LL30 HfBz4 I 5 MMAO 1.1 ABF₂₀ AA 150 90 193 184 0.45 104(2.0) LL30 ZrBz4 J 5 TIBA 1.1 ABF₂₀ AA 75 90 166 592 0.38 51 (4.2) LL30HfBz4 J 5 TIBA 1.1 ABF₂₀ AA 75 90 636 215 0.36 132 (6.3) LL30 HfBz4 J 5PMAO 1.1 ABF₂₀ AA 150 110 208 136 0.39 49 (4.9) LL38 ZrBz4 I 5 MMAO 1.1ABF₂₀ AA 75 90 163 624 0.74 6 (1.5) LL38 ZrBz4 I 5 PMAO 1.1 ABF₂₀ AA 7590 116 809 0.73 6 (1.5) LL38 TiBz4 I 5 MMAO 1.1 ABF₂₀ AA 300 90 900 110.63 533 (1.5) LL38 TiBz4 I 5 PMAO 1.1 ABF₂₀ AA 300 90 900 12 0.63 605(1.9) LL38 HfBz4 I 5 MMAO 1.1 ABF₂₀ AA 150 90 75 1579 0.75 56 (2.0) LL38HfBz4 I 5 PMAO 1.1 ABF₂₀ AA 100 90 99 1421 0.74 59 (1.9) LL39 ZrBz4 A 5MMAO 1.1 ABF₂₀ AA 50 90 901 112 0.39 5 (1.4) LL39 HfBz4 A 5 MMAO 1.1ABF₂₀ AA 50 90 901 62 0.23 34 (1.5) LL40 ZrBz4 A 5 MMAO 1.1 ABF₂₀ AA 10090 372 152 0.94 9 (1.5) LL40 TiBz4 A 5 MMAO 1.1 ABF₂₀ AA 300 90 900 130.86 38 (1.8) LL40 HfBz4 A 5 MMAO 1.1 ABF₂₀ AA 50 90 154 1120 0.95 103(1.4) LL32 ZrBz4 I 5 PMAO 1.1 ABF₂₀ AA 75 90 124 981 0.52 47 (2.3) LL32HfBz4 I 5 PMAO 1.1 ABF₂₀ AA 100 90 128 776 0.67 131 (1.7) LL45 ZrBz4 H 5MMAO 1.1 ABF₂₀ AA 150 90 227 123 0.21 3 (1.2) LL45 HfBz4 H 5 MMAO 1.1ABF₂₀ AA 300 90 150 156 0.24 8 (1.6) LL45 TiBz4 G 5 MMAO 1.1 ABF₂₀ AA300 90 900 19 0.61 2601 (2.9) LL26 ZrBz4 H 5 MMAO 1.1 ABF₂₀ AA 150 90672 46 0.35 9 (1.7) LL26 HfBz4 H 5 MMAO 1.1 ABF₂₀ AA 300 90 900 18 0.2725 (1.9) LL27 ZrBz4 H 5 MMAO 1.1 ABF₂₀ AA 150 90 312 114 0.70 36 (2.6)LL27 HfBz4 H 5 MMAO 1.1 ABF₂₀ AA 300 90 107 259 0.74 179 (1.8) LL33ZrBz4 I 5 MMAO 1.1 ABF₂₀ AA 75 90 349 231 0.57 31 (1.9) LL33 HfBz4 I 5MMAO 1.1 ABF₂₀ AA 150 90 255 169 0.57 165 (1.9) LL43 ZrBz4 H 5 MMAO 1.1ABF₂₀ AA 150 90 900 16 0.49 56 (8.0) LL43 HfBz4 H 5 MMAO 1.1 ABF₂₀ AA300 90 900 7 0.50 nd

Example 42 Propylene Polymerizations Using Isolated Complexes. A Totalof Thirty-three (33) Separate Polymerization Reactions were Performed asDescribed Herein

Preparation of the polymerization reactor prior to injection of catalystcomposition: The polymerization reactor was prepared in the mannerdescribed in Example 41.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is either a solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (“ABF₂₀”) or a solution oftris(pentafluorophenyl)borane in toluene (“BF₁₅”). The “ABF₂₀” solutionis heated to approximately 85° C. to dissolve the reagent. The molarityis indicated in the “activation method” of the individual exampledescribed below. The “group 13 reagent” solution is either a solution oftriisobutyl aluminium (“TIBA”) or a solution of trimethylaluminium(“TMA”) or a solution of triethylaluminium (“TEAL”) or a solution ofdiisobuthylaluminium hydride (“DIBAL”) or a solution of ModifiedMethylaluminoxane 3A (Azko Chemical Inc., Chicago, Ill.) (“MMAO”) or asolution of Polymethylaluminoxane-Improved Process (Azko Chemical Inc.,Chicago, Ill.) (“PMAO”), all “group 13 reagent” solutions were solutionsin toluene. The molarity of the solutions used is indicated in the“activation method” of the individual example described below.

Activation method and Injection of solutions into the pressure reactorvessel: The following methods were employed to activate and inject theisolated complexes as indicated in the Table 4. Method II: Anappropriate amount of a 0.050M solution of the group 13 reagent,containing the indicated equivalents group 13 reagent (per isolatedcomplex) in the specific examples in Table 4, is dispensed into a 1 mLvial. An appropriate amount complex solution (3–4 mM indichloroethylene) containing 0.4 mmol metal complex is added. After 10min, 0.44 mmol of the activator solution in toluene (2.5 mM) was addedto the 1 mL vial. About another 60 seconds later a fraction of the total1 mL vial contents containing the indicated “catalyst amount injected”being identified in Table 4 was injected into the pre-pressurizedreaction vessel and was followed immediately by injection of toluene toincrease the total volume injected of 0.400 mL. Method JJ: similar toMethod II except that the concentration of the group 13 reagent solutionwas 0.200 M. Method KK: similar to Method JJ except that the 1 mL vialwas heated to 50–60° C. Method LL: 40 uL of the 10 mM complex solutionin toluene is dispensed into a 1 mL vial. An appropriate amount based onthe equivalents presented in table 4 of a 0.050M solution of the group13 reagent is added. After 10 min, 0.44 mmol of the activator solutionin toluene (5 mM) was added to the 1 mL vial. About another 60 secondslater, a fraction of the total 1 mL vial contents containing theindicated “catalyst amount injected” being identified in table 4 wasinjected into the prepressurized reaction vessel and was followedimmediately by injection of toluene to increase the total volumeinjected of 0.400 mL. Method MM: An appropriate amount based on theequivalents presented in table 4 of a 0.020M solution of the group 13reagent is dispensed into a 1 mL vial. 80 uL of a complex solutioncontaining 0.4 mmol metal complex (5 mM in toluene) is added. After 50sec, an appropriate amount of the activator solution in toluene (“ABF20”is 2.5 mM and “BF15” is 5 mM), containing the indicated equivalents of“activator” (per mole isolated complex) in the specific examples intable 4, was added to the 1 mL vial. About another 60 seconds later afraction of the total 1 mL vial contents containing the indicated“catalyst amount injected” being identified in table 4 was injected intothe prepressurized reaction vessel and was followed immediately byinjection of toluene to increase the total volume injected of 0.500 mL.

Polymerization and Product work up: The polymerization reaction andproduct work up were preformed in the manner described in Example 41.

TABLE 4 catalyst complex- Group 13 Activator amount Polym. Polym.Activity (g Molecular Melting ation reagent and and mol Activationinjected temp. time polymer/ Crystallinity weight Mw point by Complexmethod mole equiv. equiv. method nmol (Celsius) (sec) (min * mmol) index(k) DSC C1 5 TEAL 1.1 ABF₂₀ MM 25 90 80 292 333 0.6 417 C1 5 TIBA 1.1ABF₂₀ MM 25 90 80 345 338 0.59 574 C1 5 MMAO 1.1 ABF₂₀ MM 25 90 80 324281 0.61 654 C1 5 MMAO 2.2 BF₁₅ MM 25 90 120 440 134 0.61 780 C1 5 TEAL1.1 ABF₂₀ MM 25 110 80 600 144 0.58 228 C1 5 TIBA 1.1 ABF₂₀ MM 25 110 80471 215 0.56 129 C2 10 DIBAL 1.1 ABF₂₀ LL 25 110 100 179 571 0.78 191 C210 DIBAL 1.1 ABF₂₀ LL 55 110 100 110 1169 0.77 121 C2 10 TMA 1.1 ABF₂₀LL 25 110 100 600 29 nd nd C2 10 TMA 1.1 ABF₂₀ LL 55 110 100 77 21290.79 84 C2 10 TIBA 1.1 ABF₂₀ LL 55 110 100 600 48 0.79 260 C3 30 DIBAL1.1 ABF₂₀ JJ 20 110 50 99 3717 0.83 165 129 C3 30 DIBAL 1.1 ABF₂₀ JJ 20130 50 90 3308 0.84 118 129 C3 30 TIBA 1.1 ABF₂₀ JJ 20 110 50 97 40130.82 222 C3 30 TIBA 1.1 ABF₂₀ JJ 20 130 50 94 3177 0.83 102 C4 5 MMAO1.1 ABF₂₀ MM 25 90 80 157 1077 0.35 527 C4 5 PMAO 1.1 ABF₂₀ MM 25 90 80141 1194 0.35 716 C4 5 TIBA 1.1 ABF₂₀ MM 20 90 80 140 1288 0.32 520 C4 5MMAO 2.2 BF₁₅ MM 25 90 80 157 985 0.3 734 C4 5 MMAO 1.1 ABF₂₀ MM 25 11080 162 717 0.36 220 C4 5 PMAO 1.1 ABF₂₀ MM 25 110 80 166 685 0.35 292 C530 DIBAL 1.1 ABF₂₀ JJ 20 110 50 179 1187 0.87 275 147 C5 30 DIBAL 1.1ABF₂₀ KK 20 130 50 318 634 0.9 113 143 C5 30 TIBA 1.1 ABF₂₀ JJ 20 110 50155 1707 0.91 246 C5 30 TIBA 1.1 ABF₂₀ KK 20 130 50 391 485 0.9 247 C610 DIBAL 1.1 ABF₂₀ II 20 110 100 263 219 0.92 58 C6 30 DIBAL 1.1 ABF₂₀JJ 20 130 200 900 34 0.93 14 C6 30 TIBA 1.1 ABF₂₀ JJ 20 110 100 487 1870.95 67 C6 30 TIBA 1.1 ABF₂₀ JJ 20 130 200 900 40 0.93 18 C7 30 DIBAL1.1 ABF₂₀ JJ 20 110 100 80 3636 0.79 315 C7 30 DIBAL 1.1 ABF₂₀ JJ 20 130200 900 131 0.8 219 C7 10 TIBA 1.1 ABF₂₀ II 20 110 100 73 3532 0.76 175C7 30 TIBA 1.1 ABF₂₀ JJ 20 130 200 900 175 0.8 274

Example 42 Ethylene-Styrene or Ethylene-1-Octene Copolymerizations UsingMetal-ligand Compositions. A Total of Twelve (12) Separateethylene-1-octene Copolymerization Reactions were Performed andThirty-nine (39) Separate ethylene-styrene Copolymerization Reactionswere Performed as Described herein

Preparation of the polymerization reactor prior to injection of catalystcomposition: A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor. The reactorwas then closed, 0.10 mL of a 0.02 M group 13 reagent solution intoluene and 3.8 mL of toluene were injected into each pressure reactionvessel through a valve. The identity of the group 13 reagent solution isMMAO. The temperature was then set to 110° C., and the stirring speedwas set to 800 rpm, and the mixture was exposed to ethylene at 100 psipressure. An ethylene pressure of 100 psi in the pressure cell and thetemperature setting were maintained, using computer control, until theend of the polymerization experiment.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (“ABF₂₀”). The solution isheated to approximately 85° C. to dissolve the reagent. The group 13reagent solution is a solution of Modified Methylaluminoxane-3A (Azko)(“MMAO”) in toluene.

In situ preparation of metal-ligand compositions: The following methodwas employed to prepare the metal-ligand compositions as indicated inthe table 5–6. Method K: An appropriate amount ligand solution (10 mM intoluene) was dispensed in a 1 mL glass vial at a scale of 0.4–0.75 mmol.To the 1 mL glass vial containing the ligand solution was added anequimolar amount of metal precursor solution (10 mM in toluene) to formthe metal-ligand composition solution. The reaction mixture was heatedto 70–80° C. for 45 min.

Activation methods and Injection of solutions into the pressure reactorvessel: The following methods were employed to activate and inject themetal-ligand compositions as indicated in the tables 5–6. Method EE: Tothe ligand metal composition (preparation described above), 20equivalents (per metal precursor equivalent) of a 500 mM solution of1-octene in toluene was added to the metal ligand composition in the 1mL vial. Then, the indicated amount of the group 13 reagent solution (50mM) was added to the 1 mL vial. This mixture was held at roomtemperature for 60–70 sec, during which time, 0.420 mL of comonomer(styrene or 1-octene) followed immediately by 0.380 mL of toluene, wereinjected into the prepressurized reaction vessel. Then, the appropriateamount of the “activator solution” (5 mM) was added to the 1 mL vial.After about 30–40 sec, a fraction of the 1 mL vial contents containingthe indicated “catalyst amount injected” were injected into the reactionvessel and was followed immediately by injection of toluene to increasethe total volume injected of 0.400–0.500 mL.

Polymerization: The polymerization reaction was allowed to continue for60–600 seconds, during which time the temperature and pressure weremaintained at their pre-set levels by computer control. The specifictimes for each polymerization are shown in tables 5–6. Thepolymerization times were the lesser of the maximum desiredpolymerization time or the time taken for a predetermined amount ofmonomer gas to be consumed in the polymerization reaction. After thereaction time elapsed, the reaction was quenched by addition of anoverpressure of carbon dioxide sent to the reactor.

Product work up: ethylene/styrene or ethylene/1-octene copolymerizationsAfter the polymerization reaction, the glass vial insert, containing thepolymer product and solvent, was removed from the pressure cell andremoved from the inert atmosphere dry box, and the volatile componentswere removed using a centrifuge vacuum evaporator. After substantialevaporation of the volatile components, the vial contents were driedthoroughly by evaporation at elevated temperature under reducedpressure. The vial was then weighed to determine the yield of polymerproduct. The polymer product was then analyzed by rapid GPC, asdescribed above to determine the molecular weight of the polymerproduced, and by FTIR or Raman spectroscopy to determine the comonomerincorporation. Results are presented in the Table 5 for ethylene-styrenecopolymerizations and Table 6 for ethylene-1-octene copolymerizations.

TABLE 5 Group 13 reagent Activator Metal complexation and mole and molactivation Ligand precursor Comonomer method equiv. equiv. method LL46ZrBz₄ Styrene K 6 MMAO 1.1 ABF₂₀ EE LL46 HfBz₄ Styrene K 6 MMAO 1.1ABF₂₀ EE LL37 ZrBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL37 HfBz₄ Styrene K 5MMAO 1.1 ABF₂₀ EE LL48 ZrBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL48 HfBz₄Styrene K 5 MMAO 1.1 ABF₂₀ EE LL31 ZrBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EELL31 HfBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL28 ZrBz₄ Styrene K 5 MMAO 1.1ABF₂₀ EE LL28 HfBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL29 ZrBz₄ Styrene K 5MMAO 1.1 ABF₂₀ EE LL29 HfBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL29 TiBz₄Styrene K 5 MMAO 1.1 ABF₂₀ EE LL30 ZrBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EELL30 HfBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL38 ZrBz₄ Styrene K 5 MMAO 1.1ABF₂₀ EE LL38 HfBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL39 ZrBz₄ Styrene K 5MMAO 1.1 ABF₂₀ EE LL39 HfBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL40 ZrBz₄Styrene K 5 MMAO 1.1 ABF₂₀ EE LL40 HfBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EELL32 ZrBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL32 HfBz₄ Styrene K 5 MMAO 1.1ABF₂₀ EE LL45 ZrBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL45 HfBz₄ Styrene K 5MMAO 1.1 ABF₂₀ EE LL26 ZrBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL26 HfBz₄Styrene K 5 MMAO 1.1 ABF₂₀ EE LL27 ZrBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EELL27 HfBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL33 ZrBz₄ Styrene K 5 MMAO 1.1ABF₂₀ EE LL33 HfBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL43 ZrBz₄ Styrene K 5MMAO 1.1 ABF₂₀ EE LL43 HfBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL1 ZrBz₄Styrene K 5 MMAO 1.1 ABF₂₀ EE LL1 HfBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EELL4 ZrBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL4 HfBz₄ Styrene K 5 MMAO 1.1ABF₂₀ EE LL7 ZrBz₄ Styrene K 5 MMAO 1.1 ABF₂₀ EE LL7 HfBz₄ Styrene K 5MMAO 1.1 ABF₂₀ EE catalyst Mol % amount Polym. Polym. Activity (gStyrene mol % injected temp. time polymer/ by linear styrene Mw (/1000)Ligand nmol (Celsius) (sec) (min * mmol) regres. by PLS (PDI) LL46 133110 174 497 12.2 5 (2.5) LL46 133 110 1366 35 14.6 3 (1.3) LL37 75 110901 162 9 bimodal LL37 75 110 901 26 14.1 bimodal LL48 150 110 323 2271.7 36 (nd) LL48 300 110 755 47 2.7 342 (nd) LL31 75 110 254 601 1 13(1.6) LL31 75 110 900 58 2.4 544 (2.0) LL28 150 110 127 809 3.4 86 (nd)LL28 300 110 289 180 5.8 209 (nd) LL29 75 110 141 1273 1.9 26 (1.9) LL2975 110 375 461 3.8 194 m (1.8) LL29 200 110 600 15 1.1 105 (5 LL30 75110 158 1172 1.9 105 (4.8) LL30 75 110 604 58 3.1 281 (2.0) LL38 75 110102 1906 1.3 26 (2.1) LL38 75 110 269 717 4.2 180 (2.2) LL39 75 110 295482 1.3 broad LL39 75 110 900 140 2.3 broad LL40 75 110 112 1817 3.4 24(2.0) LL40 75 110 259 900 11.4 207 (1.9) LL32 75 110 263 558 1.1 76(3.9) LL32 75 110 536 269 2.3 251 (2.4) LL45 150 110 178 478 3.7 21 LL45300 110 716 59 4 209 LL26 150 110 397 196 2.3 38 LL26 300 110 900 31 0.9181 LL27 150 110 900 58 0.9 195 LL27 300 110 900 35 1.5 685 LL33 75 110900 106 1 48 (2.4) LL33 75 110 900 95 1.4 307 (2.2) LL43 150 110 900 651.8 LL43 300 110 900 14 2 LL1 75 110 896 150 2.4 1346 (1.6) LL1 75 110901 112 3.6 885 (1.9) LL4 75 110 600 184 4.1 1165 (1.9 LL4 50 110 600307 8 not dissolved LL7 75 110 600 166 3 872 (1.4) LL7 50 110 600 1472.9 1732 (1.5)

TABLE 6 Group 13 catalyst Activity (g Mol % Metal reagent Activatoracti- amount Polym. Polym. polymer/ Octene Mw pre- complexation and moleand mol vation injected temp. time (min * by (/1000) Ligand cursorComonomer method equiv. equiv. method nmol (Celsius) (sec) mmol) Raman(PDI) LL7 TiBz₄ C8 K 5 MMAO 1.1 ABF₂₀ EE 200 110 600 32 8 2380 (1.4) LL7 ZrBz₄ C8 K 5 MMAO 1.1 ABF₂₀ EE 75 110 369 678 17 679 (2.3) LL7 HfBz₄C8 K 5 MMAO 1.1 ABF₂₀ EE 50 110 600 553 28 641 (4.1) LL4 TiBz₄ C8 K 5MMAO 1.1 ABF₂₀ EE 200 110 600 36 8 1341 (1.6)  LL4 ZrBz₄ C8 K 5 MMAO 1.1ABF₂₀ EE 75 110 198 1251 19 488 (2.3) LL4 HfBz₄ C8 K 5 MMAO 1.1 ABF₂₀ EE50 110 431 822 27 1706 (3.4)  LL38 TiBz₄ C8 K 5 MMAO 1.1 ABF₂₀ EE 200110 600 84 6 170 (3.7) LL38 ZrBz₄ C8 K 5 MMAO 1.1 ABF₂₀ EE 75 110 614378 12  37 (2.0) LL38 HfBz₄ C8 K 5 MMAO 1.1 ABF₂₀ EE 50 110 113 2852 15 93 (1.9) LL40 TiBz₄ C8 K 5 MMAO 1.1 ABF₂₀ EE 200 110 403 148 10 151(4.8) LL40 ZrBz₄ C8 K 5 MMAO 1.1 ABF₂₀ EE 75 110 60 4425 15  12 (1.9)LL40 HfBz₄ C8 K 5 MMAO 1.1 ABF₂₀ EE 50 110 107 3686 17  99 (2.2)

It is to be understood that the above description is intended to beillustrative and not restrictive. Many embodiments will be apparent tothose of skill in the art upon reading the above description. The scopeof the invention should, therefore, be determined not with reference tothe above description, but should instead be determined with referenceto the appended claims, along with the full scope of equivalents towhich such claims are entitled. The disclosures of all articles andreferences, including patent applications and publications, areincorporated herein by reference for all purposes.

1. A composition, comprising: a ligand characterized by the generalformula:

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰ when present is independentlyselected from the group consisting of hydride, halide, and optionallysubstituted hydrocarbyl, heteroatom-containing hydrocarbyl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, alkylthio, arylthio, thioxy,seleno, nitro, and combinations thereof; optionally two or more R groupscan combine together into ring structures, with such ring structureshaving from 3 to 100 atoms in the ring not counting hydrogen atoms; B isa bridging group having from one to 50 atoms not counting hydrogenatoms; X and X′ are the same or different and are independently selectedfrom the group consisting of oxygen, sulfur, and —PR³⁰—, where R³⁰ isselected from the group consisting of hydride, halide, and optionallysubstituted hydrocarbyl, heteroatom-containing hydrocarbyl, silyl,boryl, alkoxy, aryloxy and combinations thereof; Y and Y′ are the sameor different and are independently selected from the group consisting ofoptionally substituted amino, phosphino, hydroxy, alkoxy, aryloxy,alkylthio, arylthio and thioxy; a metal precursor compound characterizedby the general formula M(L)_(n) where M is a metal selected from groups3–6 and Lanthanide elements of the Periodic Table of Elements, each L isa moiety that forms a covalent, dative or ionic bond with M; n is 1, 2,3, 4, 5, or 6; and optionally, at least one activator.
 2. Thecomposition of claim 1, wherein the ligand is characterized by theformula:

wherein R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, and R¹⁹ are as defined above, B is as defined above, X and X′ areas defined above, and Y and Y′ are as defined above with the provisothat each of Y and Y′ include hydrogen.
 3. The composition of claim 2,wherein the ligand is characterized by the formula:

wherein each of R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ is independentlyselected from the group consisting of hydride, halide, and optionallysubstituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl,heteroalkynyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, alkylthio, arylthio, thioxy, seleno, nitro, andcombinations thereof.
 4. The composition of claim 1, wherein each of R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, and R²⁰ is independently selected from the group consisting ofhydride, halide, and optionally substituted alkyl, heteroalkyl, aryl,heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino,alkylthio, arylthio, thioxy, seleno, and nitro.
 5. The composition ofclaim 4, wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰ is independentlyselected from the group consisting of hydride, halide, and optionallysubstituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, aryloxyl,silyl, amino, alkylthio, arylthio and thioxy.
 6. The composition ofclaim 3, wherein each R² is not hydrogen.
 7. The composition of claim 6,wherein each R² is independently selected from the group consisting ofoptionally substituted aryl and heteroaryl.
 8. The composition of claim3, wherein the bridging group B is selected from the group consisting ofoptionally substituted divalent hydrocarbyl and divalent heteroatomcontaining hydrocarbyl.
 9. The composition of claim 8, wherein B isselected from the group consisting of optionally substituted divalentalkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl,aryl, heteroaryl and silyl.
 10. The composition of claim 8, wherein B isrepresented by the general formula -(Q″R⁴⁰ _(2-z″))_(z′)— wherein eachQ″ is either carbon or silicon and each R⁴⁰ may be the same or differentfrom the others such that each R⁴⁰ is selected from the group consistingof hydride and optionally substituted hydrocarbyl and heteroatomcontaining hydrocarbyl, and optionally two or more R⁴⁰ groups may bejoined into a ring structure having from 3 to 50 atoms in the ringstructure not counting hydrogen atoms; z′ is an integer from 1 to 10;and z″ is 0, 1 or
 2. 11. The composition of any of claim 1, 2, 3, 4, 5,6, 7, 8, 9 or 10 wherein M is selected from the group consisting of Hf,Zr and Ti.
 12. The composition of claim 3, wherein R⁷ and R⁸ areindependently selected from the group consisting of halo, alkoxy,aryloxy, and amino.
 13. The composition of claim 3, wherein at least oneL is an anion.